WO2020085282A1

WO2020085282A1 - Method for producing phenolic resin

Info

Publication number: WO2020085282A1
Application number: PCT/JP2019/041266
Authority: WO
Inventors: 亮介浅原; 秀治西垣
Original assignee: フタムラ化学株式会社
Priority date: 2018-10-24
Filing date: 2019-10-21
Publication date: 2020-04-30
Also published as: PH12021550649A1

Abstract

[Problem] To provide a method for producing a phenolic resin, said phenolic resin being to be used for the formation of an activated carbon adsorbent, whereby the ratio of macropores in pores formed in a resin carbide is increased by improving the composition of the phenolic resin so as to form an activated carbon adsorbent which is capable of quickly and efficiently adsorbing a low molecular compound containing nitrogen. [Solution] A method for producing a phenolic resin for forming an activated carbon adsorbent, said phenolic resin being to be carbonized and activated to form an activated carbon adsorbent. This method comprises a starting material preparation step for blending phenol with a water-soluble nylon and melting to give a starting material, and a resol preparation step for mixing the starting material with formaldehyde, a basic catalyst and an emulsifier under heating to give a nylon-containing resol resin.

Description

Method for producing phenolic resin

TECHNICAL FIELD The present invention relates to a method for producing a phenolic resin, and in particular, by improving the composition of the phenolic resin for producing an activated carbon adsorbent, carbonizing the phenolic resin to improve the performance of the activated carbon adsorbent obtained by activation. And a method for producing a phenol resin capable of

In patients with renal or liver diseases, toxic substances accumulate in the blood, resulting in encephalopathy such as uremia and disturbance of consciousness. The number of these patients tends to increase year by year. In recent years, for the treatment of these patients, an adsorbent for oral administration has been developed, which is orally ingested, adsorbs a toxic substance in the body, and excretes it out of the body (see Patent Documents 1 and 2). However, since these adsorbents are adsorbents that utilize the adsorption performance of activated carbon, they cannot be said to have sufficient adsorption capacity for toxins to be removed or selective adsorption of toxins for useful substances. Generally, activated carbon is highly hydrophobic and is not suitable for adsorbing low molecular weight ionic organic compounds such as indoxyl sulfate, DL-β-aminoisobutyric acid and tryptophan, which are represented by uremic causative substances and their precursors. The problem is included.

Therefore, in order to improve the problem of the activated carbon adsorbent, an anti-nephrotic agent composed of activated carbon obtained by forming a spherical resin compound by using wood, petroleum-based or coal-based pitches etc. as a raw material Syndrome agents have been reported (see, for example, Patent Document 3). The above-mentioned activated carbon is prepared by carbonizing and activating the petroleum hydrocarbon (pitch) or the like as a raw material to have a relatively uniform particle size. Further, an adsorbent for oral administration has been reported in which the particle size of activated carbon itself is made relatively uniform and the distribution of pore volume and the like in the activated carbon is attempted to be adjusted (see Patent Document 4). As described above, the medicinal activated carbon has a relatively uniform particle size, which improves the fluidity in the intestine, and at the same time, the pores are adjusted to improve the adsorption performance of the activated carbon. Therefore, it is taken in many patients with mild chronic renal failure.

ㆍ Medicinal activated carbon is required to adsorb substances that cause uremia and its precursors quickly and efficiently. However, the adjustment of the pores in the conventional medicinal activated carbon was not said to be good, and the adsorption performance was not stable. Therefore, the daily dose should be increased. In particular, since chronic renal failure patients have limited water intake, swallowing with a small amount of water has been a great pain for patients. In addition, in the gastrointestinal tract such as the stomach and small intestine, it is an environment in which various substances such as sugars, proteins and other compounds essential for physiological functions and enzymes secreted from the intestinal wall are mixed. Among them, a medicinal activated carbon adsorbent that rapidly adsorbs a toxic substance causing uremia and the like, particularly a nitrogen-containing compound, and excretes it out of the body with feces as it is has been desired.

The inventor scrutinized the raw material of activated carbon adsorbent before carbonization and the development of pores. As a result, by adopting a phenol resin as a resin component that is a raw material of activated carbon and devising the composition of the resin, the pores of the activated carbon derived from resin carbide are suitably controlled, and the nitrogen-containing compound of low molecular weight can be quickly and We have found an activated carbon with a pore distribution suitable for efficient adsorption.

Japanese Patent No. 3835698 JP, 2008-303193, A JP-A-6-135841 JP-A-2002-308785

The present invention has been made in view of the above points, in the phenol resin used for the production of the activated carbon adsorbent, by improving the composition of the phenol resin, to increase the proportion of macropores in the pores generated in the resin carbide. Provided is a method for producing a phenol resin for producing an activated carbon adsorbent capable of quickly and efficiently adsorbing a nitrogen-containing low molecular weight compound.

That is, the first invention is a phenolic resin for activated carbon adsorbent production which is activated by carbonization to be an activated carbon adsorbent, and water-soluble nylon is added to phenol and melted to prepare a raw material. A phenol resin characterized by comprising a raw material preparing step and a resole adjusting step of preparing a nylon-containing resole resin containing nylon by heating while mixing formaldehyde, a basic catalyst and an emulsifier in the raw material. It relates to the manufacturing method.

A second invention is a phenolic resin for producing an activated carbon adsorbent which is carbonized and activated to be an activated carbon adsorbent, wherein a raw material preparation step of adding nylon to phenol and melting it to prepare a raw material, Formaldehyde and a basic catalyst are added to a novolak resin synthesizing step of preparing a novolak resin component by heating formaldehyde, an acidic catalyst and an emulsifier while mixing the raw material, and formaldehyde and a basic catalyst in the solution obtained by the novolak resin synthesizing step. And a composite phenol resin adjusting step of adjusting the nylon-containing composite phenol resin also containing the novolak resin component by heating while mixing to synthesize a resol resin component, and a method for producing a phenol resin.

A third invention relates to the method for producing a phenol resin according to the first or second invention, wherein the amount of the nylon added is 0.5 to 5 parts by weight with respect to 100 parts by weight of phenol.

A fourth invention is an activated carbon adsorbent obtained from the nylon-containing resole resin of the first invention, which has a mercury pore volume (V1 _M ) (g / mL) at 50 to 1000 nm represented by the following formula (i). ) mercury pore volume in the _{7.5 ~ 1000nm (V2 M) (} g / mL) and the ratio of (R _V) is, according to the activated carbon adsorbent, characterized in that 0.3 to 0.6.

A fifth invention is a second activated carbon adsorbent obtained from the nylon-containing composite phenolic resin of the present invention, mercury pore volume (V1 _M) in 50 ~ 1000 nm represented by the above formula (i) (g / (mL) and the mercury pore volume (V 2 _M ) (g / mL) at 7.5 to 1000 nm (R _V ) is 0.3 to 0.8. .

A sixth invention is the oral method according to any one of the first to fifth inventions, wherein the activated carbon adsorbent is a therapeutic or prophylactic agent for orally administered renal disease or orally administered liver disease. It concerns adsorbents for administration.

According to the method for producing a phenol resin according to the first aspect of the present invention, it is a phenol resin for producing an activated carbon adsorbent which is activated by carbonization to be an activated carbon adsorbent, wherein water-soluble nylon is applied to phenol and melted. In order to have a raw material preparing step of preparing a raw material, and a resol adjusting step of preparing a nylon-containing resole resin containing nylon by heating while mixing the raw material with formaldehyde, a basic catalyst, and an emulsifier. In activated carbon derived from phenolic resin, the ratio of macropores in the pores generated in resin carbide can be increased by improving the resin composition in phenolic resin, and nitrogen-containing low molecular weight compounds can be quickly and efficiently prepared. A phenolic resin for producing an adsorbable activated carbon adsorbent can be obtained.

According to the method for producing a phenol resin according to the second aspect of the present invention, there is provided a phenol resin for producing an activated carbon adsorbent which is activated by carbonization to be an activated carbon adsorbent. In the solution obtained by the raw material preparation step of preparing, a novolak resin synthesis step of preparing a novolak resin component by heating formaldehyde to the raw material, while mixing an acidic catalyst and an emulsifier, in the solution obtained by the novolak resin synthesis step, Formaldehyde and a basic catalyst are mixed and heated to synthesize a resole resin component and to have a composite phenol resin adjustment step of adjusting a nylon-containing composite phenol resin that also contains the novolac resin component. In the activated carbon, the carbonization of the resin is improved by improving the resin composition in the phenol resin. It is possible to increase the ratio of macropores in the pores occurring, nitrogen can be obtained phenolic resin to produce a rapidly adsorbable activated carbon adsorbent low molecular compound containing.

According to the method for producing a phenol resin according to the third invention, in the first or second invention, the amount of the nylon added is 0.5 to 5 parts by weight with respect to 100 parts by weight of phenol. When the resin is used as the activated carbon adsorbent, it is possible to prevent a decrease in packing density while increasing the ratio of macropores in the pores generated in the resin carbide.

According to the activated carbon adsorbent according to a fourth aspect, the activated carbon adsorbent obtained from the nylon-containing resole resin according to the first aspect of the invention has a mercury pore volume (50 to 1000 nm in formula (i)) V1 _M) (g / mL) and the proportion of the mercury pore volume in the _{7.5 ~ 1000nm (V2 M) (} g / mL) (R V) is from 0.3 to 0.6 nitrogen It is possible to make an activated carbon adsorbent capable of rapidly adsorbing a low molecular weight compound containing a.

According to the activated carbon adsorbent according to the fifth aspect, the activated carbon adsorbent obtained from the nylon-containing composite phenolic resin according to the second aspect has a mercury pore volume at 50 to 1000 nm represented by the formula (i). Since the ratio (R _V ) of (V1 _M ) (g / mL) and mercury pore volume (V2 _M ) (g / mL) at 7.5 to 1000 nm is 0.3 to 0.8, A low-molecular compound containing nitrogen can be used as an activated carbon adsorbent capable of rapidly adsorbing.

According to the adsorbent for oral administration according to a sixth invention, in any one of the first to fifth inventions, the adsorbent for activated carbon is a therapeutic or prophylactic agent for renal disease for oral administration or liver disease for oral administration. Therefore, it has a high effect of selectively adsorbing a causative substance of renal disease or liver disease, and is suitable as a therapeutic agent or preventive agent.

It is process drawing which shows the manufacturing method of the nylon containing resole resin for activated carbon adsorbent production | generation of this invention. It is process drawing which shows the manufacturing method of the nylon containing composite phenol resin for activated carbon adsorbent production | generation of this invention. It is process drawing which shows the manufacturing method from the phenol resin manufactured by the manufacturing method of FIG. 1 and FIG. 2 to an activated carbon adsorbent.

The phenolic resin produced by the production method of the present invention is a phenolic resin used for producing an activated carbon adsorbent, and particularly a phenolic resin containing nylon. By including nylon in the phenol resin, it is possible to obtain an activated carbon adsorbent capable of adsorbing nitrogen-containing low molecular weight compounds quickly and efficiently by increasing the ratio of macropores in the pores generated in resin carbide. . First, a process for synthesizing a phenol resin, particularly a resole resin, which is a starting material for an activated carbon adsorbent will be described with reference to the process chart of FIG.

First, nylon is added to and mixed with phenol, which is the raw material for the phenolic resin, and dissolved in phenol to prepare it as the raw material (“raw material preparation process”). As the phenol resin to be subjected to the condensation reaction, a novolac resin or a resole resin can be used, and it is preferable to use the resole resin from the viewpoint of moldability, hardness, and pore preparation. In particular, since the resole resin has a higher packing density than the novolac resin, the use of an activated carbon adsorbent as a medicinal adsorbent reduces the dose volume and is useful because the burden on the patient can be reduced. Further, in a prototype example manufactured in the process diagram shown in FIG. 2 described later, a composite phenol resin in which a novolac resin and a resole resin are compounded is adopted. A composite phenol resin is useful because it improves the adsorption performance of the activated carbon adsorbent.

In the manufacturing method according to the process diagram shown in FIG. 1, nylon is preferably water-soluble nylon. According to the research conducted by the inventor, in the resole resin synthesis step described later, even if nylon was completely dissolved in phenol in the raw material preparation step, non-water-soluble nylon was precipitated in the reaction medium water, etc. This is because it was found that it was hardly contained in the prepared phenol resin. It is considered that the addition amount of nylon is preferably about 0.5 to 5 parts by weight with respect to 100 parts by weight of phenol. In the carbonization step and the activation step, if the amount is too small, the proportion of macropores in the pores generated in the resin carbide cannot be increased. On the other hand, if the amount is too large, nylon is decomposed by heat and does not remain in the fired product, so that it is considered that the packing density of the activated carbon adsorbent decreases and scatters, so that strength and adsorption performance may decrease.

Next, formaldehyde, an emulsifier, and water as a reaction medium are added and mixed, and a basic catalyst for the purpose of forming crosslinks of both molecules is added. These are subjected to dehydration condensation reaction by heating at 30 to 100 ° C. while being stirred, and spherical phenol resin is synthesized (“resole resin synthesis step”). The generated resin component is appropriately washed.

-Instead of the phenol used in the above process, an aromatic compound having a hydroxyl group is also used. Examples thereof include cresol (o-, m-, p-positions), p-phenylphenol, xylenol (2,5-, 3,5-), resorcinol and various bisphenols.

The following aldehyde compounds are used instead of the formaldehyde used in the above process. Examples include acetaldehyde, benzaldehyde, glyoxal, furfural and the like.

An amine compound is used as the basic catalyst used in the synthesis of the resole resin. Amine compounds are often used in the synthesis of resole resin components and are suitable for obtaining a stable reaction. In the prototype example, hexamethylenetetramine (hexamine, 1,3,5,7-tetraazaadamantane) and triethylenetetramine (N, N'-di (2-aminoethyl) ethylenediamine) are used. In addition to these, sodium hydroxide, magnesium hydroxide, sodium carbonate, ammonia and the like can be mentioned as the basic catalyst. The amount of basic catalyst added in the resol resin preparation step is 1 to 10% by weight based on the total amount charged in the step. The amount of addition depends on the type of basic catalyst.

-Phenolic resin becomes carbonized resin after carbonization and activation, and finally becomes an activated carbon adsorbent for oral administration. Therefore, the activated carbon adsorbent adsorbs causative substances such as uremia while smoothly flowing in the oral cavity, esophagus, stomach, duodenum, small intestine and large intestine, and is excreted from the anus along with feces. Then, a particle size or spherical shape with less resistance is a desirable shape for the convenience of smooth flow in various digestive tracts. In view of this point, it is desirable that the resin is a granular material or a spherical material from the stage of resin before carbonization.

Therefore, an emulsifier is added in the resol resin preparation process. The resole resin prepared in the same step becomes a granular material or a spherical material due to dispersion by the action of the emulsifier. As the emulsifier, water-soluble polysaccharides such as hydroxyethyl cellulose and gum arabic (gum arabic) are used. The amount of the emulsifier added is 0.1 to 5% by weight based on the total amount charged in the resol resin preparation step. The amount may be adjusted depending on the type of emulsifier and the reaction conditions.

Since an emulsifier is added, emulsification progresses through heating and stirring during the resol resin preparation process, resulting in a granular or spherical resol (phenol) resin (phenol resin particles) in the reaction liquid. It is considered that the addition of the emulsifier increases the surface tension of the reaction liquid containing phenol and the like, and minute droplets are generated to promote spheroidization. The desired size of the phenolic resin is a granular or spherical material having an average particle diameter of 200 to 700 μm. The particle size in this range is a size that allows for the volume reduction associated with the firing of carbonization described below. In addition, the resulting activated carbon adsorbent has a size suitable for oral administration.

Next, the nylon-containing composite phenolic resin preparation process according to the process diagram shown in FIG. 2 will be described. The nylon-containing composite phenol resin is a composite phenol resin composed of a novolak resin containing nylon and a resole resin. First, nylon is applied to and mixed with granular phenol, which is a raw material of a phenol resin, and the nylon is dissolved in phenol to be prepared as a raw material (“raw material preparation step”). It is considered that the addition amount of nylon is preferably about 0.5 to 5 parts by weight with respect to 100 parts by weight of phenol as in the resol resin adjusting step according to FIG.

In the raw material adjusting step for the nylon-containing resole resin shown in FIG. 1, nylon having water solubility was adopted, but the nylon in the raw material adjusting step for nylon-containing composite phenol resin shown in FIG. 2 was water-soluble nylon. Not limited to This is because nylon is dissolved in the generated novolac resin described later. Also in the prototype example described below, when normal (non-water-soluble) nylon was used, most of the nylon did not precipitate in the reaction medium water and the like, and the phenol resin contained nylon. .

Then, formaldehyde and an acid catalyst for forming a novolac resin and an emulsifier for forming a granular or spherical substance are added in advance and heated to 30 to 100 ° C. with stirring to prepare a novolac resin component (“ Novolac resin synthesis process "). In addition, reaction catalyst water is also appropriately added. Then, formaldehyde and a basic catalyst are added to a solution in which formaldehyde, an acid catalyst and an emulsifier are added to the phenol to which nylon is added. The solution contains the novolac resin produced in the previous step and unreacted phenol. The unreacted phenol remaining in the solution, the added formaldehyde and the added basic catalyst undergo a dehydration condensation reaction by heating at 30 to 100 ° C. while being stirred, and the unreacted phenol is converted into a resole resin component. Synthesized (“Composite Phenolic Resin Preparation Step”). Therefore, a composite phenol resin containing the resole resin component synthesized in the step and the novolac resin component synthesized in the previous step is prepared. The generated resin component is appropriately washed.

The phenols, alternative aromatic compounds, and alternative aldehyde compounds for formaldehyde used are the same as those described in the resole resin preparation step according to the process chart shown in FIG. An inorganic acid and an organic acid are used as the acidic catalyst. Oxalic acid was used in the prototype. Other examples of the acidic catalyst include carboxylic acids such as formic acid, dicarboxylic acids such as malonic acid, hydrochloric acid, sulfuric acid, phosphoric acid and the like.

The phenol resin (nylon-containing resole resin and nylon-containing composite phenol resin) prepared from a series of steps becomes a resin carbide through the steps shown in the process chart of FIG. 3 after appropriate washing and drying. The phenol resin is stored in a firing furnace such as a cylindrical retort electric furnace, and the inside of the furnace is kept under an inert atmosphere of nitrogen, argon, helium or the like at 300 to 1000 ° C., preferably 450 to 700 ° C. for 1 to 20 hours. When it is carbonized, it becomes a resin carbide (“carbonization step”).

After the carbonization step, the resin carbide is stored in a heating furnace such as a rotary type external heating furnace and steam activated at 750 to 1000 ° C., preferably 800 to 1000 ° C., and further 850 to 950 ° C. (“activation step”). )). The activation time is 0.5 to 50 hours, depending on the production scale, equipment, etc. Alternatively, activation of gas such as carbon dioxide is also used. The activated carbon adsorbent after activation is washed with dilute hydrochloric acid. The activated carbon adsorbent that has been washed with dilute hydrochloric acid is washed with water until the pH reaches 5 to 7, for example, by measuring the pH according to JIS K 1474 (2014).

After washing with dilute hydrochloric acid, the activated carbon adsorbent is heat-treated in a mixed gas of oxygen and nitrogen and washed with water, if necessary, to remove impurities such as ash. The residual hydrochloric acid and the like are removed by the heat treatment. Then, the amount of surface oxide of the activated carbon adsorbent is adjusted through each treatment. After the acid cleaning, the amount of surface oxides of the activated carbon adsorbent increases through the heat treatment of the activated resin carbide. The oxygen concentration during the treatment is 0.1 to 21% by volume. The heating temperature is 150 to 1000 ° C., preferably 400 to 800 ° C., and 15 minutes to 2 hours.

The resin carbide (activated carbon adsorbent) after the activation treatment or after the heat treatment subsequent to the activation treatment is preferably selected by sieving into granular or spherical activated carbon having an average particle diameter of 150 to 500 μm. By adjusting and fractionating the particle size, the adsorption rate of the activated carbon adsorbent can be made constant and the adsorption capacity can be stabilized. The range of particle diameter is not particularly limited, but if it is within the above range, swallowing by the patient (administrator) can be made smooth and the surface area of the activated carbon adsorbent can be secured. Moreover, if the particle diameters are made uniform, the adsorption performance in the digestive tract can be stabilized. Moreover, the hardness of the particles is maintained and further powdering in the digestive tract after oral administration (after taking) is suppressed. Therefore, the shape of the activated carbon of the adsorbent for oral administration is preferably spherical. However, granularity is also included because variations in sphericity due to manufacturing are also allowed.

As described above, the phenol resin (resole resin) prepared through the raw material preparation step and the resole resin preparation step in the step shown in FIG. 1 contains nylon. Nylon is a thermoplastic resin and resol resin is a thermosetting resin. Therefore, when the phenol resin particles are exposed to the heating temperature in the carbonization step, the heat resistance, the melting temperature, the volatilization amount, etc. of the nylon and the resole resin in the phenol resin particles are different from each other. Then, it is considered that the carbonization of the phenol resin particles proceeds inhomogeneously rather than becoming uniform during the firing. The resin component is volatilized from the phenol resin particles by heating and baking during carbonization. It is expected that cracks, cracks, etc. will occur in the resin carbide through this volatilization. Therefore, it is considered that macropores (about 50 nm or more) relatively easily develop in the activated carbon adsorbent derived from the resin carbide of the phenol resin.

In the process of carbonization from phenolic resin to carbonized carbon, and further activation to the activated carbon adsorbent, the weight of volatile components is reduced, obviously. Therefore, the smaller the amount of volatile components, the more the amount of carbon in the activated carbon adsorbent increases, and more dense activated carbon can be obtained. Therefore, the volatile content of the nylon-containing phenol resin is suppressed to 50% or less.

Similarly, in the step shown in FIG. 2, the nylon-containing composite phenol resin prepared through the novolak resin synthesis step and the composite phenol resin preparation step is combined with the phenol resin having different traits in both the novolac resin content and the resole resin content. Contains nylon. Among the phenolic resins, the novolac resin is a thermoplastic resin and the resol resin is a thermosetting resin. Therefore, when the composite phenol resin particles are exposed to the heating temperature in the carbonization step, the novolac resin content, the resole resin content, and the nylon in the composite phenol resin particles differ from each other in heat resistance, melting temperature, volatilization amount, and the like. At the same time, since it contains nylon having different heat resistance, melting temperature, volatilization amount, etc., it is considered that the carbonization of the composite phenol resin particles proceeds more heterogeneously rather than the carbonization accompanying the firing becomes uniform. . Carbonization decomposition gas volatilizes from the composite phenol resin particles by heating and firing during carbonization. It is expected that cracks, cracks, etc. will occur in the resin carbide through this volatilization. Therefore, it is considered that the activated carbon adsorbent derived from the resin carbide of the composite phenol resin is relatively likely to have macropores (about 50 nm or more).

Therefore, the ratio of the novolac resin component (former) and the resole resin component (latter) in the composite phenol resin (composite phenol resin particles) is 9: 1 to 5: 5. By containing the novolac resin component and the resol resin component, the proportion of macropores in the pores generated in the resin carbide can be increased. Further, by changing the ratio depending on the target substance to be adsorbed, it is possible to produce activated carbon having an arbitrary adsorption performance.

The weight of the volatiles is reduced in the process of carbonization from the composite phenol resin (composite phenol resin particles) to a resin carbide, and further activation to the activated carbon adsorbent. Therefore, the smaller the amount of volatile components, the more the amount of carbon in the activated carbon adsorbent increases, and more dense activated carbon can be obtained. Therefore, the volatile content of the composite phenol resin (composite phenol resin particles) is suppressed to 60% or less.

The nylon-containing resole resin and nylon-containing composite phenol resin have an aromatic ring structure in the molecule, so the carbonization rate increases. Furthermore, activation produces an activated carbon adsorbent having a large surface area. The activated carbon adsorbent after activation has a small pore size and a high packing density as compared with conventional activated carbon such as wood, coconut shell, and petroleum pitch. Therefore, it is suitable for adsorbing an ionic organic compound having a relatively small molecular weight (molecular weight in the range of several tens to several hundreds). Further, both phenolic resins containing nylon have less ash content such as nitrogen, phosphorus, sodium, magnesium and the like, and a higher carbon ratio per unit mass than conventional activated carbon raw materials such as wood. Therefore, an activated carbon adsorbent containing few impurities can be obtained.

ㆍ By relatively increasing the proportion of macropores, the adsorption target can easily penetrate into the activated carbon adsorbent. Then, the adsorption target is captured by the mesopores and the micropores connected to the macropores, and the adsorption proceeds rapidly. Usually, from eating to excretion, the time taken for food to be decomposed by digestion and flow in the small intestine is considered to be about 3 to 5 hours. That is, it is necessary for the adsorbent for oral administration (activated carbon adsorbent) to adsorb the nitrogen-containing low molecule that is the target of adsorption while flowing in the small intestine. Therefore, in consideration of efficient adsorption in the intestinal tract, it can be said that adsorption in a short time is desirable. From this, it is meaningful to develop many macropores of the activated carbon adsorbent.

The activated carbon adsorbent obtained from the above-mentioned production method should adsorb the causative agent of liver dysfunction and renal dysfunction listed in the prototypes described below as quickly as possible, and have sufficient adsorption performance with a relatively small dose. It is required to demonstrate. In order to find a harmonized range of properties to be provided, the activated carbon adsorbent is defined by the index of the volume ratio of the mercury pore volume value. Then, as is clear from the tendency of the prototype example described below, the suitable range value of each index is derived. The method of measuring the physical properties and the like of the activated carbon and various conditions described below will be described in detail in a prototype example.

The activated carbon adsorbent is a granular or spherical substance, and its average particle size is not particularly specified, but it is preferably 150 to 400 μm. When the size of the particles themselves is within the above range, pores such as macropores are appropriately developed, which is preferable in terms of selective adsorption. Further, since the surface area becomes appropriate, it is also preferable in terms of adsorption rate and strength.

The average particle size of the activated carbon adsorbents in the present specification and prototype examples is the particle size at an integrated value of 50% in the particle size distribution obtained by the laser diffraction / scattering method.

Mercury pore volume (V _M) is an index for evaluating the large pores of mesopores or macropores of the activated carbon. Therefore, we determined the so-called mesopores ~ macropores ranging mercury pore volume of a pore diameter range of 7.5 - 1000 nm and (V2 _M). Further, it is considered that the range of the pore diameter of 50 to 1000 nm is the effective pore size when adsorbing the adsorption target, and therefore the mercury pore volume (V1 _M ) in this range, so-called macropore range Was also calculated.

Volume ratio (R _V), the volume ratio in the activated carbon adsorbent consisting of nylon-containing resole resin represented by to equation (i) (R _V) is defined to 0.3 to 0.6. The volume ratio (R _V ) of the formula (i) is such that the nitrogen pore volume (V1 _M ) in the pore diameter range of 50 to 1000 nm (macropore) is equivalent to the nitrogen pore volume range of 7.5 to 1000 nm (mesopore). Is the quotient divided by the mercury pore volume (V2 _M ) of macropores.

In the activated carbon adsorbent made of nylon-containing composite phenol resin, the volume ratio (R _V ) is specified to be 0.3 to 0.8.

The volume ratio (R _V ) is an index showing that the ratio of macropores is high in the range of mesopores to macropores. In the case of an adsorbent such as activated carbon, micropores, mesopores, and macropores are all present. Among these, the adsorption target and performance of the activated carbon adsorbent change depending on which range of pores is developed more. The activated carbon adsorbent desired in the present invention is assumed to adsorb nitrogen-containing low molecular weight ionic organic compounds such as indoxyl sulfate, aminoisobutyric acid and tryptophan, which are represented by uremia-causing substances and precursors thereof. . And the activated carbon adsorbent of the present invention is to adsorb the molecule to be adsorbed faster than the conventional activated carbon adsorbent.

As described above, since the residence time of the activated carbon adsorbent in the small intestine is considered to be 3 to 5 hours, the adsorbent for oral administration (activated carbon adsorbent) contains nitrogen, which is the target of adsorption, in a short time. It is necessary to adsorb small molecules that do. From this, it is meaningful to develop many macropores of the activated carbon adsorbent. As disclosed in a prototype example described below, the adsorption rate increases as the numerical value of the volume ratio (R _V ) increases.

Also, the packing density of activated carbon should be 0.3 to 0.6 g / mL. If the packing density is less than 0.3 g / mL, the dose increases and it becomes difficult to swallow upon oral administration. If the packing density exceeds 0.6 g / mL, there is a risk that selective adsorption as activated carbon derived from phenol resin may not be accompanied. Therefore, the packing density is preferably in the above range.

Such an activated carbon adsorbent is a drug intended for oral administration and is a therapeutic or prophylactic agent for renal disease or liver disease. The causative substances of diseases and chronic symptoms are adsorbed and retained in the pores developed on the surface of the activated carbon adsorbent and discharged to the outside of the body, whereby the deterioration of symptoms is relieved and the pathological condition is improved. Further, in the case where there is an inborn or acquired metabolic abnormality or the possibility of the abnormality, the in-vivo concentration of the causative substance of a disease or chronic symptom can be lowered by taking an activated carbon adsorbent in advance. Therefore, it may be taken as a preventive measure to prevent the deterioration of symptoms.

Examples of renal diseases include chronic renal failure, acute renal failure, chronic pyelonephritis, acute pyelonephritis, chronic nephritis, acute nephritis syndrome, acute progressive nephritis syndrome, chronic nephritis syndrome, nephrotic syndrome, nephrosclerosis, interstitial nephritis. , Renal tubular disease, lipoid nephrosis, diabetic nephropathy, renovascular hypertension, hypertension syndrome, secondary renal diseases associated with the above-mentioned underlying diseases, and mild renal failure before dialysis. Examples of liver diseases include fulminant hepatitis, chronic hepatitis, viral hepatitis, alcoholic hepatitis, liver fibrosis, liver cirrhosis, liver cancer, autoimmune hepatitis, drug allergic liver injury, primary biliary cirrhosis, and tremor (shinshin). ), Encephalopathy, metabolic disorders, and functional disorders.

 It is difficult to specify a uniform dose when using an activated carbon adsorbent as an adsorbent for oral administration, because it is affected by age, sex, physique, or medical condition. However, in general, when it is intended for humans, it is expected that 1 to 20 g of the activated carbon adsorbent will be taken 2 to 4 times a day. The adsorbent for oral administration of the activated carbon adsorbent is administered in the form or dosage form of powder, granules, tablets, dragees, capsules, suspensions, sticks, sachets, emulsions or the like.

[Synthesis of prototype]
Nylon-containing resole resin and nylon-containing composite phenolic resin corresponding to each prototype were synthesized when preparing the activated carbon adsorbents of the prototype. Then, the respective synthesized resins were carbonized and activated to obtain a prototype activated carbon adsorbent.

Six types of nylon were used.
・ Toray Industries, Inc. AQ nylon "A-90" (water-soluble nylon)
(Hereinafter, referred to as N1.)
・ Toray Industries, Inc. AQ nylon "P-70" (water-soluble nylon)
(Hereinafter, referred to as N2.)
・ Ube Industries, Ltd. 6-nylon “1011FB”
(Hereafter referred to as N3.)
・ Ube Industries, Ltd. 6-nylon “1022B”
(Hereinafter referred to as N4.)
・ 6-Nylon “1030B” manufactured by Ube Industries, Ltd.
(Hereinafter referred to as N5.)
・ Ube Industries, Ltd. polyamide elastomer "9040X1"
(Hereinafter referred to as N6.)

<Prototype example 1>
2.7 parts by weight of nylon (N1) was added to 300 parts by weight of 90% phenol in a 1 L separable flask equipped with a stirrer and a reflux condenser and heated at 60 to 80 ° C. for 1 hour. Then, 303 parts by weight of 37% formaldehyde (formalin), 1.6 parts by weight of gum arabic as an emulsifier, 21.6 parts by weight of triethylenetetramine as a basic catalyst, and 166 parts by weight of water were charged into a separable flask. The reaction was proceeded by heating for 1 hour while maintaining the temperature. Then, it was heated to 95 ° C. or higher and refluxed for 4 hours to prepare a nylon-containing resole resin.

From the viewpoint of promoting the synthesis of the resole resin component and reducing unreacted materials, the amount of raw material is defined by the equivalence ratio (molar conversion amount). The relationship of the equivalent ratio (R1 ₁ ) between the equivalent of phenol (P1 _R ) and the equivalent of formaldehyde (F1 _R ) during the synthesis of the resole resin component was 1.3, which was derived from the formula (ii). When the equivalent ratio (R1 ₁ ) is in the range of 1.1 to 1.8, and more preferably in the range of 1.1 to 1.6, the ratio between the amount of resole resin and the amount of novolac resin becomes preferable. When the equivalence ratio (R1 ₁ ) is less than 1.1, the amount of phenol is too small, and when the equivalence ratio (R1 ₁ ) is more than 1.8, the amount of phenol is relatively excessive. The range of the equivalent ratio (R1 ₁ ) is a range in which suitable emulsion formation and the like are taken into consideration. The equivalence ratio (R1 ₁ ) of prototype 1 was 1.3.

<Prototype example 2>
A nylon-containing resol resin of Prototype Example 2 was prepared in the same manner as in Prototype Example 1 except that nylon was nylon (N2). The equivalence ratio (R1 ₁ ) of prototype example 2 was 1.3.

<Prototype example 3>
A nylon-containing resol resin of Prototype Example 3 was prepared in the same manner as in Prototype Example 2 except that the amount of nylon (N2) was 1.35 parts by weight. The equivalence ratio (R1 ₁ ) of Prototype Example 3 was 1.3.

<Prototype example 4>
A nylon-containing resole resin of Prototype Example 4 was prepared in the same manner as in Prototype Example 2 except that the amount of nylon (N2) was 8.1 parts by weight. The equivalence ratio (R1 ₁ ) of Prototype Example 4 was 1.3.

<Comparative Example 1>
300 parts by weight of 90% phenol is charged into a 1 L separable flask equipped with a stirrer and a reflux condenser, and 303 parts by weight of 37% formaldehyde (formalin), 1.6 parts by weight of gum arabic as an emulsifier, and a basic catalyst. 21.6 parts by weight of triethylenetetramine and 163 parts by weight of water were put into a separable flask and heated at 60 ° C. for 1 hour to proceed the reaction. Then, it heated at 95 degreeC or more, and refluxed for 4 hours, and prepared the resole resin. The equivalent ratio (R1 ₁ ) of Comparative Example 1 was 1.3.

<Prototype example 5>
Next, 300 parts by weight of 90% phenol and 2.7 parts by weight of nylon (N3) were put into a 1 L separable flask equipped with a stirrer and a reflux condenser, and heated at 60 to 80 ° C. for 1 hour. Then, 209.6 parts by weight of 37% formaldehyde (formalin), 1.4 parts by weight of oxalic acid as an acid catalyst, 2.7 parts by weight of gum arabic as an emulsifier, and 132.3 parts by weight of water are further added to 90 to 100 parts. The reaction was carried out at ℃ for 2 hours. Next, 93.2 parts by weight of 37% formaldehyde (formalin), 18.9 parts by weight of hexamethylenetetramine as a basic catalyst and 8.1 parts by weight of triethylenetetramine, and 40.5 parts by weight of water were placed in the separable flask. The mixture was placed in a flask and heated at 60 ° C. for 1 hour to proceed the reaction. Then, the mixture was heated to 95 ° C. or higher and refluxed for 4 hours to prepare a nylon-containing composite phenol resin of Prototype Example 5. The equivalence ratio (R1 ₁ ) of Prototype Example 5 was 1.3.

The raw material amount is also defined by the equivalence ratio (molar conversion amount) because of promotion of synthesis of the novolac resin component and reduction of unreacted substances. The relationship of the equivalent ratio (R2 ₁ ) between the equivalent of phenol (P2 _N ) and the equivalent of formaldehyde (F2 _N ) at the time of synthesis of the novolac resin component was derived from the formula (iii) and was 0.9 in the prototype example 6. Met. Equivalent ratio (R2 ₁₎ is conveniently in the synthesis of the novolak resin content be in the range of 0.9 to 0.5. When the equivalence ratio (R2 ₁ ) is less than 0.5, the amount of phenol is too small, and when the equivalence ratio (R2 ₁ ) is more than 0.9, the amount of phenol is relatively excessive. The equivalent ratio (R2 ₁ ) range is also a range in which suitable emulsion formation and the like are taken into consideration as in the equivalent ratio (R1 ₁ ).

<Prototype example 6>
A nylon-containing composite phenol resin of Prototype Example 6 was prepared in the same manner as in Prototype Example 5 except that nylon (N4) was used. The equivalence ratio (R1 ₁ ) was 1.3, and the equivalence ratio (R2 ₁ ) was 0.9.

<Prototype example 7>
The nylon-containing composite phenolic resin of Prototype Example 7 was prepared in the same manner as in Prototype Example 5 except that nylon (N5) was used. The equivalence ratio (R1 ₁ ) was 1.3, and the equivalence ratio (R2 ₁ ) was 0.9.

<Prototype example 8>
The nylon-containing composite phenol resin of Prototype Example 8 was prepared in the same manner as in Prototype Example 5 except that nylon (N6) was used. The equivalence ratio (R1 ₁ ) was 1.3, and the equivalence ratio (R2 ₁ ) was 0.9.

<Comparative example 2>
300% by weight of 90% phenol was placed in a 1 L separable flask equipped with a stirrer and a reflux condenser, 209.6 parts by weight of 37% formaldehyde (formalin), 1.4 parts by weight of oxalic acid as an acidic catalyst, and an emulsifier. Further, 3.2 parts by weight of gum arabic and 158.8 parts by weight of water were further added, and the mixture was reacted at 90 to 100 ° C. for 2 hours. Next, 93.2 parts by weight of 37% formaldehyde (formalin), 18.9 parts by weight of hexamethylenetetramine as a basic catalyst and 8.1 parts by weight of triethylenetetramine, and 40.5 parts by weight of water were placed in the separable flask. The mixture was placed in a flask and heated at 60 ° C. for 1 hour to proceed the reaction. Then, it heated at 95 degreeC or more, and refluxed for 4 hours, and prepared the nylon containing composite phenol resin. The equivalence ratio (R1 ₁ ) of Comparative Example 2 was 1.3, and the equivalence ratio (R2 ₁ ) was 0.9.

The table below shows the types of phenolic resin, equivalent ratio (R1 ₁ ), equivalent ratio (R2 ₁ ), nylon type, and nylon content (%) in the nylon-containing resole resin and nylon-containing composite phenolic resin of each prototype and comparative example. 1 and Table 2. The nylon content represents the ratio of nylon amount to phenol resin amount.

[Preparation of activated carbon adsorbent]
About the nylon-containing resol resin, the nylon-containing composite phenolic resin of the prototype, and each comparative example, each was housed in a cylindrical retort electric furnace and filled with nitrogen, and then heated to 600 ° C at 100 ° C / 1 hour. Then, the temperature was maintained at 600 ° C. for 1 hour to carbonize the phenol resin in the furnace. Then, the carbide of the phenol resin was heated to 900 ° C., steam was injected into the furnace, and the furnace was maintained at 900 ° C. for a certain period of time for activation. After activation, the product was washed with a 0.1% hydrochloric acid aqueous solution to obtain activated carbon adsorbents for each prototype and comparative example.

With respect to the activated carbon adsorbent after washing, the pH was measured by the method described in JIS K 1474 (2014), and the adsorbent was washed with water until the pH was roughly 5 to 7. The activated carbon adsorbent after washing with water was heated in a nitrogen atmosphere in a nitrogen atmosphere at 600 ° C. for 1 hour to obtain an activated carbon adsorbent corresponding to the prototype.

[Measurement item and method]
In the complex phenolic resin and activated carbon adsorbent prototype example, yield (%), the mercury pore volume of _{7.5 ~ 1000nm (V2 M) (} mL / g), mercury pore volume of 50 ~ 1000 nm (V1 _M) (ML / g), volume ratio (R _V ), nitrogen pore volume (V _H ), average particle diameter (μm), and packing density (g / mL) were measured. The results are Table 3 and Table 4.

〔yield〕
The yield (%) was obtained by measuring the weight of the resin stage before carbonization and the weight of the activated carbon adsorbent finally collected after carbonization, activation, washing and sieving to determine the amount of reduction. Then, the ratio from the initial resin weight was used.

[Mercury pore volume (V _M)]
Mercury pore volume of the activated carbon adsorbent of each prototype example and comparative examples (V _M) is manufactured by Shimadzu Corporation, using Autopore 9500, contact angle 130 °, surface tension 484 dynes /cm(4.84mN/m set), pore volume value by mercury porosimetry pore diameter _{7.5 ~ 1000nm (V2 M) (} mL / g) and pore diameter 50 to pore volume value by mercury porosimetry of 1000 nm (V1 _M ) (ML / g).

[Volume ratio (R _V )]
The volume ratio (R _V ) is, as shown in the above formula (i), the nitrogen pore volume (V1 _M ) in the pore diameter range of 50 to 1000 nm (macropore), and the pore diameter of 7.5 to. The quotient was divided by the mercury pore volume (V2 _M ) of 1000 nm.

[Nitrogen pore volume (V _H )]
For the nitrogen pore volume (V _H ) of the activated carbon adsorbents of each prototype and comparative example, the Gurvitsch's law was applied and BELSORPmini manufactured by Nippon Bell Co., Ltd. was used to convert the nitrogen adsorption into liquid nitrogen at a relative pressure of 0.953. The amount (V _ads ) was converted to the liquid volume nitrogen volume (V _H ) from the equation (iv). The method was targeted for a range of pore diameters of 0.7 to 2.0 nm. In the formula (iv), M _g is the molecular weight of the adsorbate (nitrogen: 28.020), and ρ _g (g / cm ³ ) is the density of the adsorbate (nitrogen: 0.808).

[Average particle size]
The average particle diameter (μm) of the activated carbon adsorbents of the prototype and comparative examples was measured by using a laser light scattering particle size distribution measuring device (SALD3000S) manufactured by Shimadzu Corporation, and determined by a laser diffraction / scattering method. The particle size was defined as the particle size distribution with an integrated value of 50%.

(Filling density)
The packing density (g / mL) of the activated carbon adsorbents of the prototype and comparative examples was measured according to JIS K 1474 (2014).

[Study on physical property values]
Nylon containing Prototype Examples 1-4 is activated carbon adsorbent consisting resole resin, mercury porosimetry range comparison to mesopores ~ macropores in Comparative Example 1 is activated carbon adsorbent consisting resole resin volume (V2 _M) Is large, and the mercury pore volume (V1 _M ) in the macropore range is also large. At the same time, the volume ratio (R _V ) also increased. That is, it was confirmed that many macropores were developed and the ratio was high. From the measurement of the nitrogen pore volume ( _VH ), it was also confirmed that the micropores themselves also developed a lot.

Nylon containing composite phenolic made of a resin activated carbon adsorbent Prototype Example 5-7 is, as compared to Comparative Example 2 is activated carbon adsorbent consisting composite phenolic resin, mercury pore volume _{_{(V1 M), (V2 M}} ) It was confirmed that they both increased, and it was also confirmed that the prototype example 8 was almost the same. As for the volume ratio (R _V ) in all of Prototype Examples 5 to 8, it was confirmed that many macropores developed and the ratio increased. From the measurement of the nitrogen pore volume ( _VH ), it was also confirmed that the micropores themselves also developed a lot.

The activated carbon adsorbent made of the composite phenol resin of Comparative Example 2 had a large mercury pore volume (V1 _M ) and (V2 _M ) and a high volume ratio (R _V ). It was shown that the ratio of macropores can be further increased by incorporating nylon into the composite phenolic resin, which is a raw material for the activated carbon adsorbent, as in Examples 1 to 8.

The development of macropores is due to the thermal expansion (difference in expansion coefficient) of resin components, the difference in volatilization conditions, etc., which are compounded and overlapped during the carbonization and firing of the phenol resin, and the macropores are not limited to the pores on the surface of the activated carbon, It can be inferred that the cause is the formation of pores with a depth that penetrates into.

As a result of the development of macropores, the path leading to the micropores that have adsorption capacity is expanded, and it is considered that the toxin can be easily introduced into the micropores, so the toxin can be adsorbed quickly.

[Adsorption performance evaluation]
As described above, the activated carbon adsorbent prepared through the steps of carbonization and activation of the nylon-containing resole resin and the nylon-containing composite phenolic resin of the prototype example was compared with the activated carbon adsorbent composed of the resole resin and the composite phenolic resin of the comparative example, respectively. The proportion of macropores is large. Based on this point, the inventor examined whether or not the adsorption performance with respect to a nitrogen-containing compound that could cause uremia and the like was good.

[Adsorption Performance Experiment 1]
Therefore, four types of substances, "tryptophan, indole, indole acetic acid and indoxyl sulfate" were selected as toxic substances from the nitrogen-containing low molecular weight compounds. With respect to the activated carbon adsorbents of each prototype example and comparative example, the adsorption rate (%) of the four kinds of molecules after 3 hours was measured under a vigorous stirring condition by shaking.

Regarding four kinds of adsorption rates of tryptophan, indole, indoleacetic acid and indoxyl sulfate, the above substances were dissolved in phosphate buffer of pH 7.4 to prepare a standard solution having a concentration of 0.1 g / L.
0.01 g of the spherical activated carbons of each prototype and comparative example was added to 50 mL of a standard solution of tryptophan, and contact shaking was performed at a temperature of 37 ° C. for 3 hours.
0.01 g of each spherical activated carbon of each prototype and comparative example was added to 50 mL of a standard solution of indole, and contact shaking was performed at a temperature of 37 ° C. for 3 hours.
0.01 g of each spherical activated carbon of each prototype and comparative example was added to 50 mL of a standard solution of indole acetic acid, and contact shaking was performed at a temperature of 37 ° C. for 3 hours.
0.01 g of each spherical activated carbon of each prototype and comparative example was added to 50 mL of a standard solution of indoxyl sulfuric acid, and contact shaking was performed at a temperature of 37 ° C. for 3 hours.

Thereafter, the filtrate obtained by filtration was measured for TOC concentration (mg / L) in each filtrate using a total organic carbon meter (TOC5000A, manufactured by Shimadzu Corporation), and The mass was calculated. The adsorption rate (%) of each substance to be adsorbed was obtained from the equation (v).

[Adsorption Performance Experiment 2]
In addition, since the flow time in the small intestine is approximately 3 to 5 hours, the indole adsorption rate (Ar ₁ ) after 3 hours and the indole adsorption rate after 24 hours (Ar ₁ ) Ar ₂₎ was measured and divided by the ratio (as) (% adsorption rate of indole after the 3 hours represented by the following formula (vi) (Ar ₁₎ adsorption rate of indole after 24 hours (Ar ₂₎ ) Was measured as an index of the adsorption rate of toxic substances.

500 mL of the standard solution of indole was placed in a vessel for dissolution tester and heated to a constant temperature of 37 ° C. After the temperature became stable, 0.1 g of each spherical activated carbon of each prototype and comparative example was added, and the paddle method was stirred at 100 rpm.

The filtrate obtained after filtration after 3 hours and 24 hours was measured for absorbance at 279 nm by an absorptiometry method using a spectrophotometer (UVmini-1240, manufactured by Shimadzu Corporation).

Tables 5 and 6 show the adsorption rates (%) of the above four kinds of substances as the adsorption performance experiment 1 after 3 hours and the indole as the adsorption performance experiment 2 for 3 hours for the activated carbon adsorbents of the prototypes and the comparative examples adsorption rate after (Ar ₁₎ (%) and the adsorption ratio after 24 hours (Ar ₂₎ (%), and the proportion of (Ar ₁₎ adsorption rate after 3 hours divided by the (Ar ₂₎ (As) (%)showed that.

[Results and discussion of adsorption performance]
The activated carbon adsorbents made of the nylon-containing resole resins of Prototype Examples 1 to 4 were equal to or less than the activated carbon adsorbents made of the resole resin of Comparative Example 1 with respect to any of the four types of nitrogen-containing compounds of the toxic substances used for the adsorption performance evaluation. Exhibited high adsorption performance. Regarding the ratio (As) of the adsorption rate after 3 hours obtained by dividing (Ar ₁ ) by (Ar ₂ ) as an index of the adsorption rate of indole, the activated carbon adsorbents of Prototype Examples 1 to 4 were compared with Comparative Example 1. Also demonstrated high performance. The activated carbon adsorbents made of the nylon-containing composite phenol resins of Prototype Examples 5 to 8 exhibited higher adsorption performance than the activated carbon adsorbents made of the composite phenol resin of Comparative Example 2. In addition, the adsorption rate of indole was equivalent or high. From this result, rapid and efficient adsorption proceeds even in the digestive tract after actual administration, and excretion to the outside of the body can be expected. Therefore, the activated carbon adsorbent made of the phenol resin produced according to the present invention can be an adsorbent for oral administration which is effective for the treatment and prevention of renal function, liver dysfunction and the like.

The activated carbon adsorbent produced from the phenolic resin by the production method of the present invention reaches the digestive organs by oral administration, and can rapidly adsorb nitrogen-containing compounds that cause uremia, renal function, liver dysfunction, etc. , As a therapeutic or preventive agent. Further, in the method for producing a phenol resin for producing an activated carbon adsorbent of the present invention, macropores in the activated carbon adsorbent can be efficiently developed, so that an activated carbon adsorbent having a high toxic substance adsorption performance and a high adsorption rate can be obtained.

Claims

A phenolic resin for producing an activated carbon adsorbent which is carbonized and activated to be an activated carbon adsorbent,
A raw material preparation step in which water-soluble nylon is added to phenol and melted to prepare a raw material,
A method for producing a phenol resin, comprising a step of adjusting a resole to prepare a nylon-containing resole resin containing nylon by heating formaldehyde, a basic catalyst, and an emulsifier while being mixed with the raw material.
A phenolic resin for producing an activated carbon adsorbent which is carbonized and activated to be an activated carbon adsorbent,
A raw material preparation step in which nylon is applied to phenol and melted to prepare a raw material,
Formaldehyde, a novolak resin synthesis step of preparing a novolac resin component by heating the raw material while mixing an acidic catalyst and an emulsifier,
In the solution obtained by the step of synthesizing the novolac resin, formaldehyde and a basic catalyst are mixed and heated to synthesize a resole resin component and to prepare a nylon-containing complex phenol resin also containing the novolac resin component. A method for producing a phenol resin, comprising a resin adjusting step.
The method for producing a phenolic resin according to claim 1 or 2, wherein the amount of the nylon added is 0.5 to 5 parts by weight with respect to 100 parts by weight of phenol.
An activated carbon adsorbent obtained from the nylon-containing resol resin according to claim 1,
The ratio (R) of the mercury pore volume (V1 M ) (g / mL) at 50 to 1000 nm and the mercury pore volume (V2 M ) (g / mL) at 7.5 to 1000 nm shown in the following formula (i). V ) is 0.3 to 0.6, an activated carbon adsorbent characterized by the above-mentioned.
An activated carbon adsorbent obtained from the nylon-containing composite phenolic resin according to claim 2,
The ratio (R) of the mercury pore volume (V1 M ) (g / mL) at 50 to 1000 nm and the mercury pore volume (V2 M ) (g / mL) at 7.5 to 1000 nm shown in the above formula (i). V ) is 0.3 to 0.8, and an activated carbon adsorbent.
The adsorbent for oral administration according to any one of claims 1 to 5, wherein the activated carbon adsorbent is a therapeutic or prophylactic agent for renal diseases for oral administration or liver diseases for oral administration. .