JP5590682B2 - Epoxy resin cured product porous body, water quality retaining material, antibacterial material, and method for producing epoxy resin cured product porous material - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a cured epoxy resin porous body, a water quality retaining material, an antibacterial material, and a method for producing an epoxy resin cured porous body.

  Conventionally, studies have been made on cross-linked polymer resins having a porous structure that can be used for water quality retention materials, column chromatography, and the like. As such a crosslinked polymer resin having a porous structure, a porous body made of a cured epoxy resin and a method for producing the same are disclosed. For example, in Japanese Patent Application Laid-Open No. 2008-13625 (Patent Document 1) and International Publication No. 2006/073173 (Patent Document 2), a mixed solution in which an epoxy resin and a curing agent are dissolved in an inert solvent as a porogen is used. An epoxy resin cured product porous body obtained by heating and polymerizing to obtain a cured product and then removing porogen from the cured product is disclosed.

  However, in the said patent documents 1 and 2, the epoxy resin hardened | cured material porous body which combined the alicyclic epoxy compound and the aromatic amine type hardening | curing agent, the aromatic epoxy compound and the alicyclic amine type hardening | curing agent, Although the epoxy resin cured material porous body which combined these is described, combining the alicyclic epoxy compound and the alicyclic amine-based curing agent is not described. Actually, in the above-mentioned Patent Documents 1 and 2, in the column of Examples, a porous body in which an aromatic epoxy compound and an alicyclic amine-based curing agent are combined is described, and the alicyclic epoxy compound and There is no description about a cured epoxy resin porous body combined with an alicyclic amine-based curing agent. Thus, Patent Documents 1 and 2 do not disclose a cured alicyclic epoxy resin having a porous structure obtained by combining an alicyclic epoxy compound and an alicyclic amine-based curing agent. Moreover, the conventional epoxy resin hardened | cured material porous body as described in patent documents 1-2 was not necessarily sufficient performance, when this was applied to separation media, such as column chromatography. Furthermore, the conventional cured epoxy resin porous body as described in Patent Documents 1 and 2 does not necessarily have sufficient water quality retention performance when applied to a water quality retaining material, and retains water quality at a higher level. The appearance of a porous epoxy resin cured material capable of satisfying the demand has been desired. Moreover, the conventional cured epoxy resin porous body as described in Patent Documents 1 and 2 does not necessarily provide sufficient antibacterial performance even when used as a raw material for producing antibacterial materials and antibacterial materials. .

JP 2008-13625 A International Publication No. 2006/073173 Pamphlet

  This invention is made | formed in view of the subject which the said prior art has, and is an epoxy resin hardened | cured material of the porous structure obtained by combining an alicyclic epoxy compound and an alicyclic amine hardening | curing agent, and a separation medium As a raw material for preparing antibacterial materials with sufficiently high performance, sufficiently high water quality retention performance, and sufficiently high antibacterial performance It is an object of the present invention to provide a water quality retaining material and an antibacterial material using the same, and a method for producing the same.

  As a result of intensive studies to achieve the above object, the present inventors have obtained a mixed solution containing an epoxy compound, an amine curing agent, and a solvent inert to the epoxy compound and the amine curing agent. In the method for producing an epoxy resin cured product by removing the solvent from a cured product obtained by heating, an alicyclic epoxy compound having three or more epoxy groups in one molecule is used as the epoxy compound, and Surprisingly, by using an alicyclic amine curing agent as the amine curing agent, the epoxy resin curing with a porous structure despite the use of the alicyclic epoxy compound and the alicyclic amine curing agent. Product (epoxy resin cured product porous body) is obtained, and such epoxy resin cured product porous product has sufficiently high performance as a separation medium, and has sufficiently high water quality retention performance, Also found that becomes available as a raw material for preparing an antimicrobial material having a duck sufficiently high antibacterial performance, and have completed the present invention.

  That is, the epoxy resin cured product porous body of the present invention includes an alicyclic epoxy compound having three or more epoxy groups in one molecule, an alicyclic amine curing agent, the alicyclic epoxy compound, and the alicyclic ring. A cured epoxy resin cured product obtained by heating a mixed solution containing a solvent inert to the formula amine curing agent to obtain a cured product, and then removing the solvent from the cured product. is there.

  In the epoxy resin cured product porous body of the present invention, the alicyclic epoxy compound is represented by the following general formula (1):

[In the formula (1), X represents an alicyclic hydrocarbon group having 3 to 8 carbon atoms which is bonded to the nitrogen atom (N) in the formula directly or via a linear alkylene group having 1 to 5 carbon atoms. Y represents an epoxy group bonded to the nitrogen atom (N) in the formula directly or via a linear alkylene group having 1 to 5 carbon atoms, and m and n are such that the total number of Y is 3 or more. M is an integer selected from 2 to 4, n is each independently an integer of 1 or 2, p is independently an integer of 0 or 1, The sum of p and n is 2. ]
It is preferable that it is a compound represented by these.

  Moreover, in the epoxy resin hardened | cured material porous body of the said invention, the said alicyclic epoxy compound is the following general formula (2)-(3):

It is preferable that it is at least 1 sort (s) among the compounds represented by these.

  Furthermore, in the epoxy resin cured product porous body of the present invention, the alicyclic amine curing agent is preferably an alicyclic amine compound having two or more primary amino groups in the molecule, isophorone diamine, More preferably, it is at least one selected from the group consisting of menthanediamine, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane, and modified products thereof.

  In the cured epoxy resin porous body of the present invention, the solvent is preferably at least one selected from polyalkylene glycol having a hydroxyl value of 50 mgKOH / g or more and derivatives thereof.

  The water quality holding material of the present invention comprises the above-mentioned cured epoxy resin porous material of the present invention. Moreover, the 1st antimicrobial material of this invention is equipped with the epoxy resin hardened material porous body of the said invention.

  Furthermore, the 2nd antibacterial material of this invention is equipped with the quaternized amine containing epoxy porous body obtained by quaternizing the amino group in the epoxy resin hardened | cured material porous body of the said invention.

  Moreover, the manufacturing method of the epoxy resin hardened material porous body of the present invention includes an alicyclic epoxy compound containing three or more epoxy groups in one molecule, an alicyclic amine curing agent, and the alicyclic epoxy compound. And a mixed solution containing a solvent inert to the alicyclic amine curing agent to obtain a cured product, and then removing the solvent from the cured product to obtain a porous epoxy resin This is a method for obtaining a cured product.

  According to the present invention, it is a cured epoxy resin product having a porous structure obtained by combining an alicyclic epoxy compound and an alicyclic amine curing agent, and has a sufficiently high performance as a separation medium and a sufficiently high water quality. Epoxy resin cured product porous body that can be used as a raw material for preparing antibacterial materials having retention performance and sufficiently advanced antibacterial performance, a method for producing the same, and water quality retention using the same It becomes possible to provide a material and an antibacterial material.

2 is a scanning electron micrograph of a cured epoxy resin porous material obtained in Example 1. FIG. 2 is a scanning electron micrograph of a cured epoxy resin porous material obtained in Example 2. FIG. 4 is a scanning electron micrograph of a cured epoxy resin porous material obtained in Example 3. FIG. It is a scanning electron micrograph of the epoxy resin hardened material porous body obtained in Examples 4-7. It is a scanning electron micrograph of the epoxy resin hardened material porous body obtained in Examples 8-11. FIG. 2 is a chromatogram measured when alkylbenzenes were separated using a capillary column made of a cured epoxy resin material obtained in Example 1. FIG. It is a graph which shows the relationship between the density | concentration of the organic solvent in a mobile phase, and the retention coefficient (k) of a solute at the time of using as a separation medium of the epoxy resin hardened | cured material porous body obtained in Example 1. FIG. The turbidity of water in the cup into which cut flowers were inserted when the water quality holding material comprising the cured epoxy resin obtained in Example 12 and Comparative Examples 2 to 3 was used and when the water quality holding material was not used. It is a graph which shows the relationship between and elapsed days. It is a scanning electron micrograph of the epoxy resin hardened | cured material obtained in Examples 13-15. It is a scanning electron micrograph of the epoxy resin hardened material obtained in Comparative Examples 4-9. It is a photograph which shows the form of the organism on the bacteria culture sheet | seat which dripped the sample water (water 10 minutes after antibacterial material addition) in the beaker in the case of using the antibacterial material obtained in Example 17. It is a photograph which shows the form of the organism on the bacteria culture sheet | seat which dripped the sample water (water 10 minutes after antibacterial material addition) in the beaker using the antibacterial material obtained in the comparative example 11. It is a photograph which shows the form of the living body on the bacterial culture sheet | seat which dripped the sample water (water which passed 10 minutes after preparation) in the beaker at the time of not using an antibacterial material.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

  First, the manufacturing method of the epoxy resin hardened material porous body of the present invention and the epoxy resin hardened material porous body of the present invention will be described. That is, the epoxy resin cured product porous body of the present invention includes an alicyclic epoxy compound having three or more epoxy groups in one molecule, an alicyclic amine curing agent, the alicyclic epoxy compound, and the alicyclic ring. A cured epoxy resin cured product obtained by heating a mixed solution containing a solvent inert to the formula amine curing agent to obtain a cured product, and then removing the solvent from the cured product. is there. Thus, the epoxy resin cured product porous body of the present invention is obtained by utilizing the above-described method for producing a cured epoxy resin cured product of the present invention. The “porous structure” as used herein refers to the structure of the porous body formed by the above production method, and is a non-particle aggregation type structure in which the columnar epoxy resin cured product is branched in three dimensions. (Three-dimensional network structure: so-called co-continuous structure) is preferable.

  In the present invention, an alicyclic epoxy compound having 3 or more (more preferably 3 to 5, particularly preferably 4) epoxy groups in one molecule is used. Thus, by using an alicyclic epoxy compound having three or more epoxy groups in one molecule, a alicyclic epoxy compound and an alicyclic amine curing agent that could not be produced conventionally are combined. It is possible to produce a cured epoxy resin having a porous structure (particularly preferably a three-dimensional network structure). When the number of epoxy groups in one molecule of such an alicyclic epoxy compound is less than 3, a cured epoxy resin cured product having a porous structure is produced when an alicyclic epoxy compound and an alicyclic amine curing agent are combined. I can't do it.

  Moreover, it does not restrict | limit especially as such an alicyclic epoxy compound which has 3 or more epoxy groups in 1 molecule, The thing which has an alicyclic hydrocarbon group and 3 or more epoxy groups is utilized suitably can do. Furthermore, as such an alicyclic epoxy compound having three or more epoxy groups in one molecule, from the viewpoint of developing higher antibacterial properties, the alicyclic epoxy compound contains an N atom. It is preferable to use a material having the following general formula (1):

[In the formula (1), X represents an alicyclic hydrocarbon group having 3 to 8 carbon atoms which is bonded to the nitrogen atom (N) in the formula directly or via a linear alkylene group having 1 to 5 carbon atoms. Y represents an epoxy group bonded to the nitrogen atom (N) in the formula directly or via a linear alkylene group having 1 to 5 carbon atoms, and m and n are such that the total number of Y is 3 or more. M is an integer selected from 2 to 4, n is each independently an integer of 1 or 2, p is independently an integer of 0 or 1, The sum of p and n is 2. ]
The compound represented by these is more preferable.

  X in the general formula (1) is bonded to the nitrogen atom (N) in the formula directly or via a linear alkylene group having 1 to 5 carbon atoms (more preferably 1 to 3 and even more preferably 1). It is an alicyclic hydrocarbon group having 3 to 8 carbon atoms (more preferably 4 to 7 and still more preferably 5 to 6). The linear alkylene group that may exist between the nitrogen atom (N) and the alicyclic hydrocarbon group is a methylene group, an ethylene group, a propylene group, or the like. When the value exceeds the upper limit, the mechanical strength of the porous body tends to decrease. As such X, for example, when m in the formula is 2, the following formulas (I) to (VI):

The substituent represented by these may be sufficient.

  Y in the general formula (1) is bonded to the nitrogen atom (N) in the formula directly or via a linear alkylene group having 1 to 5 (more preferably 1 to 3, more preferably 1) carbon atoms. It is an epoxy group. Such linear alkylene groups are the same as those described for X.

  In the general formula (1), m and n are integers selected so that the total number of Y is 3 or more. When the total number of Y is less than 3, the number of epoxy groups in the compound is less than 3. Moreover, m in such a formula (1) is an integer in any one of 2-4 (more preferably 2). When the numerical value of m is less than the lower limit, the crosslinking reaction tends to be insufficient. On the other hand, when the upper limit is exceeded, the reactivity tends to decrease due to steric hindrance. Moreover, n in the said Formula (1) is an integer of 1 or 2 each independently (more preferably 2). If such a numerical value is less than the lower limit, the crosslinking reaction tends to be insufficient. On the other hand, if the upper limit is exceeded, the reactivity tends to decrease due to steric hindrance. Moreover, p in the said General formula (1) is an integer of 0 or 1 each independently. Such a value of p indicates the number of hydrogen atoms (H) bonded to the nitrogen atom (N) in the formula (1). Therefore, p and n existing in one bracket are p when the number of bonds (n) of the epoxy group (Y) to the nitrogen atom (N) is 1, and the number of bonds of the epoxy group (Y) ( When n) is 2, p is 0. Thus, in the above general formula (1), the sum of p and n existing in one parenthesis is 2.

  Examples of the alicyclic epoxy compound having three or more epoxy groups in one molecule include the following general formulas (2) to (3):

At least one of the compounds represented by the formula is particularly preferred.

  The alicyclic amine curing agent is not particularly limited as long as it can be used as a curing agent when producing an epoxy resin, and a compound having an alicyclic hydrocarbon group and an amino group is appropriately used. it can. Such an alicyclic amine curing agent is preferably an alicyclic amine compound having two or more primary amino groups in the molecule from the viewpoint of achieving an efficient crosslinking reaction, More preferably, it is at least one selected from the group consisting of menthanediamine, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane, and modified products thereof. Bis (4-amino-3-methylcyclohexyl) methane and bis (4-aminocyclohexyl) methane are particularly preferred. Examples of such modified amines include epoxy-modified products, carboxylic acid-modified products, urea-modified products, modified products using ketone compounds, modified products using silane compounds, and the like. What modified the cyclic amine compound by the well-known method can be used suitably.

  The solvent used in the present invention is a solvent inert to the alicyclic epoxy compound and the alicyclic amine curing agent. Since such a solvent is inactive with respect to the alicyclic epoxy compound and the alicyclic amine curing agent, it is possible to cause reaction-induced phase separation (spinodal phase separation). It is one that can form a co-continuous structure (sponge-like structure) with an epoxy-based polymer by heat polymerization (that can be used as a so-called “porogen (pore forming agent)”). That is, such a solvent is present in a polymerization reaction that forms a porous polymer at a certain stage of polymerization, and is removed from the reaction mixture at a predetermined stage to thereby obtain a porous structure (particularly preferably a three-dimensional structure). It is possible to obtain a porous epoxy resin cured product having a network skeleton structure).

  As such a solvent, it is more preferable that the solvent can dissolve the alicyclic epoxy compound and the alicyclic amine curing agent. Examples of such a solvent include cellosolves such as methyl cellosolve and ethyl cellosolve, esters such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate, or glycols such as polyethylene glycol and polypropylene glycol. Such a solvent can be used individually by 1 type or in combination of 2 or more types.

  Such a solvent is preferably at least one selected from polyalkylene glycols having a hydroxyl value of 50 mgKOH / g or more (more preferably 100 to 1000 mgKOH / g) and derivatives thereof. If the hydroxyl value is less than the lower limit, the viscosity of the solvent becomes high, and it becomes difficult to make the pore diameter of the formed epoxy cured product porous body sufficiently large, or the hydrophilicity of the epoxy resin cured product porous body. Tend to decrease.

  Furthermore, the content ratio of the alicyclic epoxy compound and the alicyclic amine curing agent in the mixed solution is such that the amino group in the curing agent is 0 with respect to 1 equivalent of the epoxy group in the alicyclic epoxy compound. It is preferable to be 3 to 1.2 equivalents (more preferably 0.5 to 1.0 equivalents). If the equivalent ratio of the curing agent is less than the lower limit, the crosslinking density of the epoxy resin cured product tends to be low, and heat resistance, solvent resistance, etc. tend to decrease. On the other hand, if the upper limit is exceeded, unreacted amino groups , And the curing agent tends to remain in the cured product unreacted or hinder the improvement of the crosslinking density.

  Moreover, it is preferable that the content rate of the said solvent in the said liquid mixture is 50-90 mass%, and it is more preferable that it is 60-80 mass%. When the content of such a solvent is less than the lower limit, a porous structure tends not to be formed. On the other hand, when the content exceeds the upper limit, the porosity tends to be too high and the mechanical strength tends not to be maintained.

  Further, in such a mixed solution, a curing accelerator may be further added. As such a curing accelerator, known ones can be used as appropriate, for example, tertiary amines such as triethylamine and tributylamine, 2-phenol-4-methylimidazole, 2-ethyl-4-methylimidazole, Imidazoles such as 2-phenol-4,5-dihydroxymethylimidazole and the like may be used.

  In addition, the method for preparing such a mixed solution is not particularly limited, and a method of mixing the alicyclic epoxy compound, the alicyclic amine curing agent and the solvent at room temperature or while heating may be adopted. Alternatively, a method may be employed in which a mixture of the alicyclic epoxy compound and the alicyclic amine curing agent is added to the solvent and mixed or dissolved at room temperature or while heating.

  The process of obtaining such a cured product by heating such a mixed liquid and the process of removing the solvent from the cured product will be described below.

  In such a step of heating the mixed solution (heating step), the heating conditions such as the heating temperature, time, and pressure of the mixed solution in obtaining the cured product are the alicyclic epoxy compound and the alicyclic amine. There are no particular limitations as long as it is a condition that allows the curing agent to react to form a porous structure. In addition, such heating conditions are different depending on the type and amount of the alicyclic epoxy compound, the alicyclic amine curing agent and the solvent (porogen) to be used, and cannot be generally described. The temperature is preferably 50 to 200 ° C, more preferably 130 to 170 ° C, and the heating time is preferably 60 to 360 minutes, more preferably 120 to 240 minutes. If the heating temperature and time are less than the lower limit, the reaction tends to be difficult due to a crosslinking reaction, whereas if the upper limit is exceeded, the reaction rate tends to be too high and a porous structure tends not to be formed. In addition, the said heating temperature means the temperature of the said liquid mixture. Therefore, for example, when polymerizing by heating in a dryer, there is a difference between the temperature setting of the dryer and the true temperature of the mixed solution. It is necessary to do. In addition, such heating conditions (temperature, pressure, time) are preliminarily tested by changing the type and amount of the alicyclic epoxy compound, the alicyclic amine curing agent, and the solvent (porogen) with an electron microscope. The optimum conditions for obtaining the desired porous structure (three-dimensional network structure) may be obtained by confirming the structure by, for example, and appropriately determined based on the result.

  In addition, when the cured product is obtained, if the crosslinking reaction of the polymerization component (polymer component) of the alicyclic epoxy compound and the curing agent does not proceed sufficiently, the resulting porous material is separated by liquid chromatography. When used as a medium, the number of theoretical plates tends to be low. Therefore, when a porous body is used as a separation medium, it tends not to function sufficiently. Therefore, when obtaining such a cured product, after-curing may be performed after the heat treatment from the viewpoint of allowing the crosslinking reaction to proceed more sufficiently. As such an after-curing method, it is preferable to employ a method of performing a high-temperature treatment for a short time (treatment at 70 to 200 ° C. for about 30 to 120 minutes). In addition, such after-curing is performed before removing the solvent from the cured product because it tends to cause shrinkage in the cured epoxy resin and change the porous structure when performed after the solvent is removed. It is preferable. Moreover, when the said solvent is a low boiling point thing, you may perform an after cure after substituting to a high boiling point solvent.

  Furthermore, the method for removing the solvent from the cured product after obtaining such a cured product may be any method that can remove the solvent from the cured product, and is not particularly limited. The cured product is taken out from the mixed solution, and the solvent is removed by immersing it in water. The cured product is taken out from the mixed solution and immersed in an organic solvent capable of dissolving the solvent. The solvent is removed, and the cured product is taken out from the mixed solution, immersed in an organic solvent capable of dissolving the solvent, and then immersed in water and washed to remove the solvent. A method capable of removing the solvent, such as a method, can be appropriately employed.

  In addition, although the said alicyclic epoxy compound and the said alicyclic amine hardening | curing agent are combined and used by the manufacturing method of such an epoxy resin hardened | cured material porous body of this invention, the epoxy resin of a porous structure is used. Although the reason why the cured product can be produced is not necessarily clear, the present inventors speculate as follows. That is, first, when the mixed liquid is heated to polymerize the alicyclic epoxy compound and the alicyclic amine curing agent, the solvent is used for the alicyclic epoxy compound and the alicyclic amine curing agent. Therefore, when the polymerization proceeds and the polymer component increases, spinodal phase separation occurs and a co-continuous structure (sponge-like structure) is formed. When the polymer component undergoes a crosslinking reaction before phase separation further proceeds and the co-continuous structure disappears, the structure is frozen and fixed to form a three-dimensional network structure (porous structure). It is guessed. Therefore, in order to obtain a cured product having a porous structure, it is necessary to advance the crosslinking reaction before the co-continuous structure disappears, and it is necessary to increase the speed of the crosslinking reaction. In the present invention, since an alicyclic epoxy compound having three or more epoxy groups in one molecule is used, the alicyclic epoxy compound and the alicyclic amine curing agent are combined, It is presumed that the crosslinking reaction can proceed at a sufficient rate, thereby achieving the formation of a three-dimensional network structure. Then, when the solvent is removed from the cured product in which such pores are formed, it is presumed that pores are formed at locations where the solvent was present, and a cured epoxy resin product having a porous structure is obtained. The

In addition, the cured epoxy resin porous body of the present invention thus obtained preferably has a porosity of 20% to 90%, more preferably 60 to 80%. When the porosity is less than the lower limit, when the cured epoxy resin porous material is used as a separation medium, the porosity tends to be too low and the practicality tends to be insufficient, and on the other hand, exceeds the upper limit. However, the strength of the porous body is lowered and the practicality tends to be lowered. In addition, as the porosity of the porous body, the following formula:
[Porosity (%)] = (1−W / ρV) × 100
(Wherein, W represents the dry weight (g) of the porous body, V represents the apparent volume (cm ³ ) of the porous body, and ρ represents the true density (g / cm ³ ) of the resin.)
The value obtained by calculating is adopted. In addition, as the “true density of the resin” in the above formula, a value measured in accordance with JIS-K7112 (B method I) after defoaming the porous body in ethanol is adopted.

  Moreover, in such an epoxy resin hardened | cured material porous body, it is preferable that an average pore diameter is 0.5-50 micrometers, and it is more preferable that it is 1-10 micrometers. If the average pore diameter is less than the lower limit, the pores are likely to be clogged due to clogging and the like, and the pressure during liquid feeding is set to a high pressure when used for applications that allow liquid to permeate (separation medium, etc.). When it exceeds the said upper limit, it exists in the tendency for the intensity | strength of a porous body to fall.

  In addition, the porosity and average pore diameter of such a cured epoxy resin material are the type of alicyclic epoxy compound, alicyclic amine curing agent and solvent (porogen) used, and the mixture thereof. The content varies depending on the content ratio and heating conditions. Therefore, in order to obtain a cured epoxy resin porous body having a target design, a phase diagram of the system may be prepared in advance, and optimal conditions may be selected as appropriate according to the target design (structure).

  Moreover, the shape in particular of the said epoxy resin hardened | cured material porous body is not restrict | limited, According to the use, it can be set as arbitrary shapes, such as a sheet form, rod shape, and cylinder shape.

  Moreover, since the cured epoxy resin porous material of the present invention is a cured product of an epoxy resin, it has a functional group on the surface and can be subjected to surface modification according to the purpose by a graft reaction or the like. . Furthermore, since the porous epoxy resin cured product according to the present invention is three-dimensionally cross-linked, it is excellent in chemical resistance and heat resistance and can be used even in harsh environments.

  Moreover, the cured epoxy resin porous material of the present invention is suitably used for a separation medium (for example, a packing medium for a column for liquid chromatography) in addition to a water quality retaining material and an antibacterial material described below. Can do.

  As mentioned above, although the manufacturing method of the epoxy resin hardened | cured material porous body and epoxy resin hardened | cured material porous body of this invention was demonstrated, hereafter, the water quality holding material of this invention is demonstrated.

  The water quality holding material of the present invention comprises the above-mentioned cured epoxy resin porous material of the present invention. Such a water quality holding material should just be equipped with the epoxy resin hardened | cured material porous body of the said invention, and another structure is not restrict | limited in particular. As such other components, known materials that can be used for the water quality retaining material can be used in appropriate combination.

  Moreover, what is necessary is just to utilize the water quality holding | maintenance material of this invention, in order to hold | maintain water quality, for example, you may use as freshness maintenance materials, such as a cut flower, or as a freshness maintenance material of the water in a water tank. The reason why the water quality retaining material of the present invention can exhibit excellent water quality retaining performance is not necessarily clear, but when used as an example for a freshness retaining material such as cut flowers, it will be discharged from cut flowers. In addition to purifying water as a result of adsorption and retention of aging-promoting substances and wastes in the pores of the cured epoxy resin porous material, the cured epoxy resin porous material of the present invention has sufficient antibacterial performance. The present inventors infer that this is because the bacteria in water can be sufficiently sterilized. In addition, the water quality retaining material of the present invention is easy to handle, environmentally friendly and hygienic.

  Further, when the water quality retaining material of the present invention is used as a freshness retaining material such as cut flowers, from the viewpoint of obtaining a higher effect, the entire cured epoxy resin porous body in the water quality retaining material of the present invention is submerged in water. It is preferable to use a part of the water which is not submerged in water. As described above, the reason why a higher effect can be obtained by using a part of the cured epoxy resin porous body on the water surface is not necessarily clear, but water evaporates from the surface of the porous body on the water surface. As a result, the amount of pumped water in the porous body increases, and the substance adsorbed by the porous body in the water is pushed up to the upper part of the water. As a result, the surface of the porous body in the underwater part is always kept in a state with little adsorbed material. For this reason, the present inventors speculate. As described above, when the water quality retaining material of the present invention is used for a freshness retaining material such as cut flowers, the water with cut flowers etc. can always be kept clear without frequent water change, and cut flowers due to impurities. This eliminates the occlusion of the conduit and constantly clears the cut flower stem so that the freshness of the cut flower can be maintained for a long time.

  In addition, the form of the water quality retaining material of the present invention is not particularly limited, and the design may be appropriately changed according to the method of use and the like. For example, the water quality retaining material of the present invention may be molded into a filter shape, a tube shape, a rod shape or the like and placed in water for use.

  Next, the first and second antibacterial materials of the present invention will be described. The 1st antibacterial material of this invention is equipped with the epoxy resin hardened material porous body of the said invention. Such a 1st antibacterial material should just be equipped with the epoxy resin hardened | cured material porous body of the said invention, and another structure is not restrict | limited in particular. As such other components, known materials that can be used for antibacterial materials can be used in appropriate combination.

  The second antibacterial material of the present invention comprises a quaternized amine-containing epoxy porous body obtained by quaternizing the amino group in the cured epoxy resin porous body of the present invention. Thus, by quaternizing the amino group, it becomes possible to exhibit more advanced sterilization performance. Moreover, such a 2nd antimicrobial material should just be equipped with the said quaternized amine containing epoxy porous body, and another structure is not restrict | limited in particular. Moreover, as such other components, known materials that can be used for antibacterial materials can be used in appropriate combination.

  Furthermore, the method for quaternizing the amino group in such a cured epoxy resin cured material is not particularly limited, and a known method capable of quaternizing the amino group can be appropriately employed. For example, the cured epoxy resin porous material is immersed in a known amine quaternizing agent such as hydrochloric acid aqueous solution, nitric acid aqueous solution, phosphoric acid aqueous solution, sulfuric acid aqueous solution, acetic acid aqueous solution, etc. You may employ | adopt the method of advancing a classification reaction.

  In addition, when the amino group is quaternized, the quaternizing agent is sufficiently introduced into the pores of the cured epoxy resin porous body to sufficiently quaternize the amino group present in the porous body. From the viewpoint of making the quaternizing agent and the amino group sufficiently contacted, after immersing the porous epoxy resin cured body in the quaternizing agent, irradiating with ultrasonic waves Also good.

  In addition, the method of using the first and second antibacterial materials of the present invention is not particularly limited. For example, the first and second antibacterial materials can be used together with building materials by coating or kneading on building materials such as building interior and exterior walls, floors, ceilings, and bran. Alternatively, it may be widely used for medical instruments, cooking utensils, sinks, ventilation fans, air conditioning equipment, footwear, and the like.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

Example 1
First, a reaction tube was prepared in which an inner wall of a capillary tube having a length of 0.1 mm and a length of 1000 mm was coated with a thin film of 3-aminopropyltriethoxysilane. Next, 0.93 g of an alicyclic epoxy compound represented by the above general formula (3) (hereinafter simply referred to as “TETRAD-C” in some cases), the following general formula (4):

0.38 g of alicyclic amine (bis (4-aminocyclohexyl) methane, manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter simply referred to as “BACM”), polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) 4.0 g of a hydroxyl value of 380 mg KOH / g: hereinafter sometimes simply referred to as “PEG 300”), and after sufficiently mixing these under atmospheric pressure at room temperature, vacuum deaeration to prepare a mixed solution did. Next, the mixed solution was poured into the reaction tube, sealed at both ends of the tube, and a sealed container filled with the mixed solution was obtained. Thereafter, the sealed container is put into an oil bath having a temperature of 140 ° C. (constant), heated for 4 hours, and reacted (polymerized) with TETRAD-C and BACM in the mixed solution to obtain a cured epoxy resin. Was formed. Next, the sealed container was taken out from the oil bath and cooled to room temperature. Next, by using a liquid delivery pump for liquid chromatography, methanol is fed into the capillary tube, and polyethylene glycol is removed, so that a porous epoxy resin cured product (epoxy resin cured product porous body) is formed in the capillary tube. ) The porosity of the epoxy resin cured product thus obtained was 70%, and the average pore diameter was 1.2 μm.

(Example 2)
Except that the temperature of the oil bath was changed to 150 ° C., a porous epoxy resin cured product (epoxy resin cured porous material) was obtained in the same manner as in Example 1. The porosity of the cured epoxy resin obtained as described above was 70%, and the average pore diameter was 1.0 μm.

(Example 3)
Except that the temperature of the oil bath was changed to 135 ° C., a cured epoxy resin material (epoxy resin cured material porous body) having a porous structure was obtained in the same manner as in Example 1. The porosity of the epoxy resin cured product thus obtained was 70%, and the average pore diameter was 1.5 μm.

<Confirmation of structure of cured epoxy resin obtained in Examples 1 to 3>
Scanning electron micrographs of the cured epoxy resin porous bodies obtained in Examples 1 to 3 are shown in FIGS. As is clear from the scanning electron micrographs shown in FIGS. 1 to 3, the cured epoxy resin porous material (Examples 1 to 3) of the present invention is a combination of an alicyclic epoxy compound and an alicyclic amine. Although it was obtained, a three-dimensional network skeleton structure was formed, and it was confirmed that the cured epoxy resin had a porous structure. Moreover, it was confirmed that the epoxy resin hardened | cured material porous body obtained in Examples 1-3 has the space | gap which all connect. In addition, as apparent from the results shown in FIGS. 1 to 3, in the case of producing a cured epoxy resin porous body by combining an alicyclic epoxy compound and an alicyclic amine, by changing the temperature, It was also found that the structure such as the pore size can be changed.

(Examples 4 to 7)
Example 1 except that the amount of PEG 300 used was 3.6 g (Example 4), 4.0 g (Example 5), 4.2 g (Example 6), and 4.4 g (Example 7), respectively. In the same manner as above, a cured epoxy resin product having a porous structure (epoxy resin cured product porous body) was obtained.

<Confirmation of structure of cured epoxy resin obtained in Examples 4 to 7>
Scanning electron micrographs of the cured epoxy resin porous bodies obtained in Examples 4 to 7 are shown in FIG. As apparent from the scanning electron micrograph shown in FIG. 4, the cured epoxy resin porous material of the present invention (Examples 4 to 7) was obtained by combining an alicyclic epoxy compound and an alicyclic amine. In spite of this, a three-dimensional network skeleton structure was formed, and it was confirmed that the cured epoxy resin had a porous structure. In addition, as apparent from the results shown in FIG. 4, in the case of producing a cured epoxy resin porous material by combining an alicyclic epoxy compound and an alicyclic amine, the amount of the solvent (PEG 300) used It was also found that the structure such as the pore diameter can be changed by changing.

(Examples 8 to 11)
Example 1 except that the amount of BACM used was 0.34 g (Example 4), 0.36 g (Example 5), 0.38 g (Example 6), and 0.4 g (Example 7), respectively. Similarly, a cured epoxy resin product having a porous structure (epoxy resin cured product porous body) was obtained.

<Confirmation of structure of cured epoxy resin obtained in Examples 8 to 11>
Scanning electron micrographs of the cured epoxy resin porous bodies obtained in Examples 8 to 11 are shown in FIG. As is clear from the scanning electron micrograph shown in FIG. 5, the cured epoxy resin porous material (Examples 8 to 11) of the present invention is obtained by combining an alicyclic epoxy compound and an alicyclic amine. In spite of this, a three-dimensional network skeleton structure was formed, and it was confirmed that the cured epoxy resin had a porous structure. Further, as apparent from the results shown in FIG. 5, in the case of producing a cured epoxy resin porous body by combining an alicyclic epoxy compound and an alicyclic amine, the alicyclic amine (BACM) to be used is used. It has also been found that the structure such as the pore diameter can be easily changed by changing the amount of.

(Comparative Example 1)
Instead of TETRAD-C, the following general formula (5):

1.6 g of a non-alicyclic epoxy compound represented by the formula (hereinafter referred to as “TEPIC” in some cases) is used, the amount of BACM used is changed to 0.37 g, and polyethylene glycol (Nacalai) is used instead of PEG 300. Made by Tesque Co., Ltd., hydroxyl value 550 mg KOH / g: Hereinafter, 7.0 g of “PEG 200” is used in some cases, and the oil bath temperature (reaction temperature) is changed from 140 ° C. to 80 ° C. In the same manner as in Example 1, a cured epoxy resin porous material for comparison was obtained. In addition, as a result of the measurement by a scanning electron microscope, such a cured epoxy resin was confirmed to have a porous structure.

[Evaluation of characteristics of porous bodies obtained in Example 1 and Comparative Example 1]
<Evaluation of separation performance>
The performance as a separation medium was evaluated by using the cured epoxy resin porous material obtained in Example 1 and the cured epoxy resin cured material obtained in Comparative Example 1 as chromatography. That is, the capillary tube in which each porous body is formed is a capillary column, pentylbenzene is used as the solute a below, butylbenzene is used as the solute b below, and uracil is used as the non-retaining solute. Using a mixed solvent of acetonitrile and water as the mobile phase, injecting the solute into the column under the conditions of a flow rate of 1.0 μL / min and a temperature of 30 ° C., and detecting the elution time with a UV detector The retention times of a and b and the retention time of the non-retained solute were measured respectively and the following formula:
[Retention coefficient of solute (k)] = {(Retention time of solute) − (Retention time of non-retention solute)} / (Retention time of non-retention solute)
[Separation coefficient α _{(a / b)} ] = (Retention coefficient of solute a) / (Retention coefficient of solute b)
_Was calculated to obtain the value of the separation factor (α _{(pentylbenzne / butylbenzene)} ), and the performance as a separation medium was evaluated. In addition, such a value of α indicates that the larger the value, the higher the hydrophobicity.

As a result of measurement of such a separation factor, the separation factor (α _{(pentylbenzne / butylbenzene)} ) of the cured epoxy resin obtained in Example 1 is 2.74, which is obtained using TEPIC in Comparative Example 1. The resulting cured epoxy resin porous material had a separation factor (α _{(pentylbenzne / butylbenzene)} ) of 1.04. From such a result, the hydrophobicity of the cured epoxy resin material (Example 1) of the present invention is greatly improved in hydrophobicity as compared with the cured cured epoxy resin material (Comparative Example 1). It was confirmed. Thus, the cured epoxy resin porous material of the present invention (Example 1) is separated from the material using hydrophobic interaction as compared with the cured epoxy resin cured material (Comparative Example 1). Was found to be very useful as a separation medium. Such an improvement in hydrophobicity is an effect obtained by using an alicyclic epoxy compound and an alicyclic amine curing agent as a raw material for the porous body. The present inventors infer that the effect is achieved by using a combination of cyclic amine curing agents.

In order to confirm the separation performance of the cured epoxy resin porous material of the present invention (Example 1), a capillary column in which the cured epoxy resin material is formed inside the capillary tube obtained in Example 1 was used. Attempts were made to separate alkylbenzenes. As such alkylbenzenes, benzene, toluene, ethylbenzene, propylbenzene, butylbenzene, pentylbenzene, and hexylbenzene were used. At the time of separation of such alkylbenzenes _may, CH 3 CN 60 volume% and 20mM sodium phosphate buffer (pH: 7.0) 40% by volume of the mixture _{(CH 3 CN / buffer = 60} /40 (V / v)) was used as the mobile phase and the injection volume was 10 nL. The obtained result is shown in FIG. In FIG. 6, peak 1 indicates benzene, peak 2 indicates toluene, peak 3 indicates ethylbenzene, peak 4 indicates propylbenzene, peak 5 indicates butylbenzene, and peak 6 indicates pentylbenzene. Peak 7 represents hexylbenzene.

  As is clear from the results shown in FIG. 6, it was confirmed that the cured epoxy resin porous material of the present invention (Example 1) functions sufficiently as a separation medium and can sufficiently separate alkylbenzenes. Moreover, when the theoretical plate number of the epoxy resin cured material porous body (Example 1) obtained in Example 1 was determined, it was found that the theoretical plate number was 10,000 or more, and the porous body had sufficiently high performance as a separation column. It was also found to have.

Furthermore, in order to evaluate the properties of the cured epoxy resin porous material obtained in Example 1 as a separation medium, CH ₃ CN 60% by volume and 20 mM sodium phosphate buffer (pH: 7.0) 40% by volume. (CH ₃ CN / buffer = 60/40 (v / v)) as a mobile phase, and cytosine, adenine, uracil, thymine, benzene, and toluene as solutes, respectively. The organic solvent concentration was changed, and the retention coefficient of each solute was determined for each concentration. In addition, the retention coefficient of each solute was calculated | required by measuring the elution time of each solute and calculating the calculation formula of the retention coefficient (k) of the said solute. The obtained results are shown in FIG.

  As is clear from the results shown in FIG. 7, it was found that the property of retaining a hydrophobic substance is high under the condition where the concentration of the solute is low. It can be seen that this is due to the contribution of hydrophobic interaction in the cured epoxy resin porous material obtained in Example 1. On the other hand, it was found that the property of retaining the hydrophilic compound is high under the condition where the concentration of the solute is high. This shows that the typical hydrophilic interaction contributes to the cured epoxy resin porous material obtained in Example 1. From these results, it was confirmed that the cured epoxy resin porous material of the present invention (Example 1) has both hydrophilic and hydrophobic properties, and is very useful as a separation medium for various substances. It was confirmed that it was useful.

(Example 12)
The amount of TETRAD-C used was 17.4 g, the amount of BACM used was 11.2 g, the amount of PEG 300 used was 71.4 g, and instead of a capillary tube, a cylindrical Teflon (inner diameter 12 mm, length 150 mm) The same procedure as in Example 1 except that when a polyethylene glycol was extracted and removed, the cured epoxy resin was taken out of the Teflon (registered trademark) tube and subjected to ultrasonic cleaning using acetone. As a result, a cured epoxy resin porous body was obtained. In addition, as a result of the measurement by a scanning electron microscope, such a cured epoxy resin was confirmed to have a porous structure. The porosity of the cured epoxy resin obtained as described above was 75%, and the average pore diameter was 2.0 μm.

(Comparative Example 2)
23.2 g of bisphenol A type epoxy resin (trade name “Epicoat 828” manufactured by Japan Epoxy Resin Co., Ltd.) and 5.2 g of BACM are polyethylene glycol (manufactured by Nacalai Tesque Co., Ltd., hydroxyl value 550 mg KOH / g: in some cases, It is simply referred to as “PEG 200”.) Dissolved in 71.6 g and vacuum degassed to obtain a mixed solution, which was poured into a cylindrical Teflon (registered trademark) tube having an inner diameter of 12 mm and a length of 150 mm. The stopper was put in, and the mixture was placed in a 120 ° C. oil bath as it was and polymerized in the oil bath for 1 hour. Thereafter, the glass tube is taken out from the oil bath, cooled to room temperature, the polymer is taken out from the tube made of Teflon (registered trademark), and immersed in water at 60 ° C. for 20 hours to extract and remove polyethylene glycol. An aromatic epoxy resin cured product porous body was obtained. In addition, as a result of the measurement by a scanning electron microscope, such a cured epoxy resin was confirmed to have a porous structure. The porosity of the cured epoxy resin obtained as described above was 70%, and the average pore diameter was 1.0 μm.

(Comparative Example 3)
Bisphenol A type epoxy resin (Japan Epoxy Resin Co., Ltd., trade name “Epicoat 828”) 20.2 g and polyaminoamide curing agent (Fuji Kasei Kogyo Co., Ltd., trade name “Tomide 245-S”, amine value 535) 8 6 g of each is dissolved in 71.2 g of PEG 200 (hydroxyl value 550 mg KOH / g) and vacuum degassed to obtain a mixed solution, which is a cylindrical tube made of Teflon (registered trademark) having an inner diameter of 12 mm and a length of 150 mm. Then, the mixture was put into a stopper, put in a 60 ° C. oil bath as it was, and polymerized in the oil bath for 1 hour, and then the temperature of the oil bath was raised to 100 ° C. and further heated for 1 hour. Thereafter, the tube made of Teflon (registered trademark) is taken out from the oil bath, cooled to room temperature, the polymer is taken out from the glass tube, and immersed in water at 50 ° C. for 20 hours to extract and remove polyethylene glycol. An aromatic epoxy resin cured product porous body was obtained. In addition, as a result of the measurement by a scanning electron microscope, such a cured epoxy resin was confirmed to have a porous structure. The porosity of the cured epoxy resin obtained as described above was 70%, and the average pore diameter was 1.0 μm.

[Evaluation of properties of cured epoxy resin obtained in Example 12 and Comparative Examples 2-3]
<Evaluation of water quality retention performance>
Water was poured into four glass cups (diameter 50 mm, height 100 mm) to a height of 50 mm, and roses were inserted into each glass cup. In one cup (hereinafter referred to as “Cup A”), the cured epoxy resin porous material (diameter: 12 mm, length: 120 mm) obtained in Example 12 was replaced with another cup (hereinafter referred to as “Cup B”). The epoxy resin cured product porous body (diameter 12 mm, length 120 mm) obtained in Comparative Example 2 was obtained in Comparative Example 2, and the other cup (hereinafter referred to as “Copp C”) was obtained in Comparative Example 3. The cured epoxy resin porous body (diameter 12 mm, length 120 mm) was inserted so that each part was in contact with air. Further, the last cup (hereinafter referred to as “Copp D”) into which no porous body was inserted was used as it was. And the turbidity of the water in the cups AD was confirmed by visual observation at the stage where a predetermined number of days had elapsed, and the turbidity was relatively evaluated. A graph showing the relationship between elapsed days and turbidity is shown in FIG.

  As is clear from the results shown in FIG. 8, in the cured epoxy resin porous material of the present invention (Example 12), no turbidity was confirmed even after 14 days, and the results were obtained in Comparative Examples 2-3. It was confirmed that the water quality was maintained at a sufficiently high level as compared with the obtained cured epoxy resin porous material. Moreover, in the epoxy resin hardened | cured material porous body (Example 12) of this invention, since the turbidity of water does not change as mentioned above, it turns out that sufficient bactericidal effect with respect to the microbe in water is acquired. From such a result, it turned out that the epoxy resin hardened | cured material porous body (Example 12) of this invention is useful as a water quality maintenance material or an antibacterial material.

(Example 13)
0.93 g of an alicyclic epoxy compound represented by the above general formula (2) (hereinafter sometimes simply referred to as “BDAC”), and an alicyclic amine (BACM) represented by the above general formula (4) 0.47 g and 3.6 g of polyethylene glycol (PEG 300) were prepared, and these were sufficiently mixed under atmospheric pressure at room temperature and degassed to prepare a mixed solution. Next, the mixed solution was poured into the reaction tube (inner diameter 12 mm, length 150 mm), sealed at both ends of the tube, and a sealed container filled with the mixed solution was obtained. Thereafter, the sealed container is put into an oil bath having a temperature of 140 ° C. (constant) and heated for 4 hours. In the sealed container, BDAC and BACM in the mixed solution are reacted (polymerized) to form an epoxy. A cured product of the resin was obtained. Next, the sealed container was taken out from the oil bath and cooled to room temperature. Next, the cured product is removed from the sealed container, the cured product is ultrasonically washed in acetone, and polyethylene glycol is extracted and removed from the cured product to obtain a porous epoxy resin cured product (cured epoxy resin product). Porous material: indicated as “BDB01” in FIG.

(Example 14)
Except that the temperature of the oil bath was set to 150 ° C., a porous epoxy resin cured product (epoxy resin cured porous body: indicated as “BDB02” in FIG. 9) was obtained in the same manner as in Example 13.

(Example 15)
Except that the temperature of the oil bath was 160 ° C., a porous epoxy resin cured product (epoxy resin cured porous body: indicated as “BDB03” in FIG. 9) was obtained in the same manner as in Example 13.

(Comparative Example 4)
Instead of BDAC, the following general formula (6):

1.11 g of an alicyclic epoxy compound represented by the following (hereinafter referred to as “HBADE” in some cases) was used, the amount of BACM used was changed to 0, 29, and instead of PEG 300, manufactured by Wako Pure Chemical Industries, Ltd. For comparison, in the same manner as in Example 13 except that 3.6 g of polyethylene glycol (hydroxyl value 190 mgKOH / g: hereinafter, simply referred to as “PEG 600”) was used and the oil bath temperature was 160 ° C. An epoxy resin cured product (shown as “HB01” in FIG. 10) was obtained.

(Comparative Example 5)
A cured epoxy resin product (shown as “HB02” in FIG. 10) for comparison was obtained in the same manner as in Comparative Example 4 except that the temperature of the oil bath was set to 170 ° C.

(Comparative Example 6)
A cured epoxy resin product (shown as “HB03” in FIG. 10) for comparison was obtained in the same manner as in Comparative Example 4 except that the temperature of the oil bath was 180 ° C.

(Comparative Example 7)
In the same manner as in Comparative Example 4 except that 3.6 g of polyethylene glycol (hydroxyl value 110 mg KOH / g: hereinafter sometimes referred to simply as “PEG 1000”) manufactured by Wako Pure Chemical Industries, Ltd. was used instead of PEG 600. An epoxy resin cured product (shown as “HB04” in FIG. 10) was obtained.

(Comparative Example 8)
A cured epoxy resin product (shown as “HB05” in FIG. 10) for comparison was obtained in the same manner as in Comparative Example 7 except that the temperature of the oil bath was set to 170 ° C.

(Comparative Example 9)
An epoxy resin cured product for comparison (shown as “HB06” in FIG. 10) was obtained in the same manner as in Comparative Example 7 except that the temperature of the oil bath was changed to 180 ° C.

<Confirmation of structure of cured epoxy resin obtained in Examples 13 to 15 and Comparative Examples 4 to 9>
The structures of the cured epoxy resins obtained in Examples 13 to 15 and Comparative Examples 4 to 9 were measured with a scanning electron microscope. Scanning electron micrographs of the cured epoxy resins obtained in Examples 13 to 15 are shown in FIG. Moreover, the scanning electron micrograph of the epoxy resin hardened | cured material obtained by Comparative Examples 4-9 is shown in FIG.

  As is clear from the results shown in FIG. 9, it was confirmed that all of the cured epoxy resin porous material (Examples 13 to 15) of the present invention had a three-dimensional network structure. On the other hand, the epoxy resin cured products for comparison (Comparative Examples 4 to 9) were all in the form of particles and had a structure in which the particles were aggregated. From these results, when an alicyclic epoxy compound (HBADE) having only two epoxy groups in one molecule is used, a porous structure (three-dimensional network structure) can be obtained by changing various synthesis conditions. It was found that an epoxy resin cured product) could not be obtained. In order to produce a cured epoxy resin product having a porous structure by combining an alicyclic epoxy compound and an alicyclic amine, an alicyclic epoxy compound having at least three epoxy groups in one molecule is used. It turns out that it is necessary to use.

(Example 16)
7.44 g of the alicyclic epoxy compound (BDAC) represented by the above general formula (2), 3.7 g of the alicyclic amine (BACM) represented by the above general formula (4), polyethylene glycol (PEG 300 36.8 g) was prepared, and these were sufficiently mixed at room temperature under atmospheric pressure and degassed to prepare a mixed solution. Next, the mixed solution was poured into a Teflon (registered trademark) tube (inner system 12 mm, length 150 mm), sealed at both ends of the tube, and the interior was filled with the mixed solution. A sealed container was obtained. Thereafter, the sealed container is put into an oil bath having a temperature of 140 ° C. (constant) and heated for 3 hours to react (polymerize) BDAC and BACM in the mixed solution to obtain a cured epoxy resin. It was. Next, the sealed container was taken out from the oil bath and cooled to room temperature. Next, the cured product is removed from the sealed container, the cured product is ultrasonically washed in acetone to extract and remove polyethylene glycol from the cured product, and a porous epoxy resin cured product (epoxy resin cured product) is obtained. A porous material) was obtained. In addition, when the obtained epoxy resin hardened | cured material was observed with the scanning electron microscope, it was confirmed that the said epoxy resin hardened | cured material is a porous body which has a three-dimensional network structure. Moreover, the porosity of the epoxy resin hardened material thus obtained was 76%, and the average pore diameter was 1.5 μm.

(Example 17)
After the epoxy resin cured product porous body obtained in Example 16 was completely dried, it was immersed in a 1.0 N hydrochloric acid aqueous solution, reacted with ultrasonic irradiation for 15 minutes, and the amino group in the porous body was Was quaternized to obtain a quaternized amine-containing epoxy porous body.

(Comparative Example 10)
10.1 g of bisphenol A type epoxy resin (Japan Epoxy Resin Co., Ltd., trade name “Epicoat 828”) and polyaminoamide curing agent (Fuji Kasei Kogyo Co., Ltd., trade name “Tomide 245-S”, amine value 535) 4 .2 g were dissolved in 35.7 g of PEG 200 (hydroxyl value 550 mg KOH / g), respectively, and vacuum degassed to obtain a mixed solution. Next, the mixed solution is injected into a Teflon (registered trademark) tube (inner diameter: 12 mm, length: 150 mm), plugged, put into an oil bath at 60 ° C. and heated for 1 hour, and then an oil bath. The temperature was raised to 100 ° C. and further heated for 1 hour. Thereafter, the cured product is taken out from a Teflon (registered trademark) tube, immersed in water at 50 ° C. for 20 hours, and polyethylene glycol is extracted and removed to obtain a cured aromatic epoxy resin porous body for comparison. It was. In addition, as a result of the measurement by a scanning electron microscope, such a cured epoxy resin was confirmed to have a porous structure. Moreover, the porosity of the epoxy resin hardened material thus obtained was 70%, and the average pore diameter was 1.0 μm.

(Comparative Example 11)
After the epoxy resin cured porous body obtained in Comparative Example 10 was completely dried, it was immersed in a 1.0 N aqueous hydrochloric acid solution and irradiated with ultrasonic waves for 15 minutes to react with the porous body. The amino group was quaternized to obtain a quaternized amine-containing epoxy porous material for comparison.

[Evaluation of characteristics of porous bodies obtained in Example 17 and Comparative Example 11]
<Evaluation of antibacterial performance>
Antibacterial performance was evaluated using the quaternized amine-containing epoxy porous body obtained in Example 17 and the quaternized amine-containing epoxy porous body for comparison obtained in Comparative Example 11 as antibacterial materials, respectively. That is, first, water used for cut flowers was purely diluted 100 times to obtain sample water containing bacteria. Next, 50 mL of the sample water was put into three beakers to obtain beakers A to C into which the sample water was introduced. Next, each quaternized amine-containing epoxy porous body obtained in Example 17 and Comparative Example 11 was cut to 4.1 g, and the beaker A was quaternized amine obtained in Example 17. The antibacterial material (4.1 g) made of the containing epoxy porous body was charged, and the antibacterial material (4.1 g) made of the quaternized amine-containing epoxy porous material obtained in Comparative Example 11 was put into the beaker B. In addition, none of the antibacterial materials were used in the beaker C. And after adding each antibacterial material, each sample water in beakers A to C after 10 minutes has passed is dropped onto a bacterial culture sheet (trade name “Petrifilm”: manufactured by 3M) to culture the bacteria. Then, the amount of bacteria was examined to evaluate the antibacterial performance of each antibacterial material. In addition, even after 4 days, each sample water was collected in the same manner to cultivate bacteria, and the amount of bacteria was examined. The photograph which shows the form of the organism on the bacteria culture sheet which dripped the sample water (water 10 minutes after antibacterial material addition) in the beaker using the antibacterial material obtained in Example 17 is shown in FIG. A photograph showing the form of the organism on the bacterial culture sheet in which the sample water in the beaker using the antibacterial material obtained in step (water 10 minutes after addition of the antibacterial material) was dropped is shown in FIG. 12, and the antibacterial material was not used. The photograph which shows the form of the organism on the bacterial culture sheet | seat which dripped the sample water (water which passed 10 minutes after preparation) in a beaker is shown in FIG. In addition, Table 1 shows the number of bacteria when the sample water in each beaker after 4 days is used. The number of bacteria is a number obtained by counting the number of colonies colored in the bacterial culture sheet.

  As is clear from the results shown in FIGS. 11 to 13, when the antibacterial material of the present invention (Example 17) was used, no bacteria were confirmed in the sample water 10 minutes after the addition of the antibacterial material. On the other hand, even when the antibacterial material for comparison (Comparative Example 11) was used, the number of bacteria in the sample water 10 minutes after the addition of the antibacterial material was smaller than when the antibacterial material was not used (FIG. 13). It was recognized that there was a bactericidal effect. However, when the antibacterial material for comparison (Comparative Example 11) and the antibacterial material of the present invention (Example 17) are compared, the antibacterial material for comparison (Comparative Example 11) does not necessarily have a sufficient bactericidal effect. I understood that. In addition, the bacterial culture sheet | seat when not using an antibacterial material as shown in FIG. 13 was colored in the whole background, and there existed bacteria that could not be counted. Further, as is clear from the results shown in Table 1, when the antibacterial material of the present invention (Example 17) was used, the generation of bacteria was sufficiently suppressed, and the antibacterial material of the present invention (Example 17). ) Was confirmed to have a sufficiently high bactericidal effect even when compared with a comparative antibacterial material (Comparative Example 11). From these results, it was found that the antibacterial material of the present invention (Example 17) has a very high sterilization performance.

  As described above, according to the present invention, it is a cured epoxy resin product having a porous structure obtained by combining an alicyclic epoxy compound and an alicyclic amine curing agent, and has sufficiently high performance as a separation medium. A cured epoxy resin porous body that can be used as a raw material when preparing an antibacterial material having a sufficiently high water quality retention performance and a sufficiently high antibacterial performance, and a method for producing the same, and It becomes possible to provide a water quality retaining material and an antibacterial material using the same. Therefore, the cured epoxy resin porous material of the present invention can be suitably used for various separation media, water quality retention materials, antibacterial materials, and the like.

Claims (9)

  An alicyclic epoxy compound having three or more epoxy groups in one molecule, an alicyclic amine curing agent, and a solvent inert to the alicyclic epoxy compound and the alicyclic amine curing agent. After obtaining the cured product by heating the mixed liquid containing, by removing the solvent from the cured product, to obtain a porous epoxy resin cured product that is a cured epoxy resin of a porous structure, the epoxy resin A quaternized amine-containing epoxy resin porous body obtained by quaternizing an amino group in a cured product porous body. The alicyclic epoxy compound has the following general formula (1):
[In the formula (1), X represents an alicyclic hydrocarbon group having 3 to 8 carbon atoms which is bonded to the nitrogen atom (N) in the formula directly or via a linear alkylene group having 1 to 5 carbon atoms. Y represents an epoxy group bonded to the nitrogen atom (N) in the formula directly or via a linear alkylene group having 1 to 5 carbon atoms, and m and n are such that the total number of Y is 3 or more. M is an integer selected from 2 to 4, n is each independently an integer of 1 or 2, p is independently an integer of 0 or 1, The sum of p and n is 2. ]
The quaternized amine-containing epoxy resin porous body according to claim 1, which is a compound represented by: The alicyclic epoxy compound has the following general formulas (2) to (3):
The quaternized amine-containing epoxy resin porous body according to claim 1 or 2, which is at least one of the compounds represented by formula (1).   The quaternized amine-containing epoxy according to any one of claims 1 to 3, wherein the alicyclic amine curing agent is an alicyclic amine compound having two or more primary amino groups in the molecule. Resin porous body.   The alicyclic amine curing agent is selected from the group consisting of isophorone diamine, menthane diamine, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane, and modified products thereof. The quaternized amine-containing epoxy resin porous body according to any one of claims 1 to 4, which is at least one kind.   The quaternized amine-containing product according to any one of claims 1 to 5, wherein the solvent is at least one selected from a polyalkylene glycol having a hydroxyl value of 50 mgKOH / g or more and a derivative thereof. Epoxy resin porous body.   A water quality holding material comprising the quaternized amine-containing epoxy resin porous body according to any one of claims 1 to 6.   An antibacterial material provided with the quaternized amine containing epoxy resin porous body as described in any one of Claims 1-6.   An alicyclic epoxy compound containing three or more epoxy groups in one molecule, an alicyclic amine curing agent, a solvent inert to the alicyclic epoxy compound and the alicyclic amine curing agent; After obtaining a cured product by heating a mixed solution containing, an epoxy resin cured product porous body that is a cured epoxy resin product having a porous structure is obtained by removing the solvent from the cured product, and the epoxy A method for producing a quaternized amine-containing epoxy resin porous body, wherein a quaternized amine-containing epoxy porous body is obtained by quaternizing an amino group in a cured resin porous body.