JP2008024904A - Anti-cedar pollen allergen composition, method for producing the same and anti-cedar pollen allergen member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an excellently safe anti-cedar pollen allergen composition in which effectiveness for an anti-cedar pollen allergen is confirmed and efficient and inexpensive supply thereof can be afforded, to provide a method for producing the composition and to provide an anti-cedar pollen allergen member. <P>SOLUTION: The anti-cedar pollen allergen composition comprises a lignophenol derivative containing at least a phenol derivative having 2 number of phenolic hydroxy groups and having a 1,1-bisarylpropane unit in which carbon atoms at the o- and/or p-positions with respect to the phenolic hydroxy group of the phenol derivative are bound to the carbon atom at the C1 position of the arylpropane unit of lignin. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an anti-cedar pollen allergen composition that inactivates a cedar pollen allergen present in a living environment, a method for producing the same, and an anti-cedar pollen allergen member.

  Sugi pollinosis patients are overwhelmingly common among seasonal allergic conjunctivitis patients, and it is estimated that it now reaches 15% of the total population. In recent years, research has been advanced from the viewpoint of denaturation and adsorption of proteins that are constituents of allergens, and various antiallergen compositions have been proposed (for example, Patent Documents 1 and 2).

JP 2003-81727 A Japanese Patent Laid-Open No. 2-16731

  Patent Documents 1 and 2 propose using polyvinylphenol, polytyrosine or tannic acid as an allergen reducing agent.

  However, Patent Document 1 uses a synthetic compound, and Patent Document 2 says that the composition is a naturally-derived substance, and although it is effective for reducing allergens, it is universally effective for all allergens. I didn't mean. In fact, cedar pollen allergens and other plant-derived allergens have been shown to be significantly involved in the sugar chain, unlike other antigens. Conformations that act specifically on anti-cedar pollen allergens It is necessary to develop and formulate a member with a structure with

  On the other hand, the anti-cedar pollen allergen composition, as well as other anti-allergen compositions, had to be excellent not only in efficacy but also in terms of economy and safety.

  The present invention meets the above requirements, and the effectiveness of the cedar pollen allergen is confirmed, and the anti-cedar pollen allergen composition, its production method, and the anti-cedar pollen allergen member, which are excellent in safety and can be efficiently and inexpensively provided. The purpose is to provide.

In order to achieve the above object, the gist of the invention described in claim 1 is that at least a phenol derivative having 2 phenolic hydroxyl groups is included, the carbon derivative at the C1 position of the arylpropane unit of lignin is bonded to the phenol derivative. An anti-cedar pollen allergen composition comprising a lignophenol derivative having a 1,1-bisarylpropane unit to which an ortho-position and / or a para-position carbon atom of the phenolic hydroxyl group is bonded. An anti-cedar pollen allergen composition according to a second aspect of the present invention is the first aspect, wherein the phenol derivative is catechol or resorcinol.
The gist of the invention described in claim 3 is that the phenol derivative having two phenolic hydroxyl groups is mixed with one and the carbon derivative at the C1 position of the arylpropane unit of lignin is related to the phenol derivative. An anti-cedar pollen allergen composition comprising a lignophenol derivative having a 1,1-bisarylpropane unit to which a carbon atom at the ortho-position and / or para-position of a phenolic hydroxyl group is bonded.
The gist of the invention described in claim 4 is that the number of phenolic hydroxyl groups of the phenol derivative is 2, and the ortho-position of the phenolic hydroxyl group and / or the carbon atom at the C1 position of the arylpropane unit of lignin and / or An anti-cedar pollen allergen member comprising an anti-cedar pollen allergen composition containing a lignophenol derivative having a 1,1-bisarylpropane unit bonded with a para-position carbon atom, held on a substrate. The gist of the invention described in claim 5 is that the phenol derivative having two phenolic hydroxyl groups is mixed with one and the carbon derivative at the C1 position of the arylpropane unit of lignin is related to the phenol derivative. An anti-cedar pollen allergen composition containing a lignophenol derivative having a 1,1-bisarylpropane unit bonded with an ortho-position and / or a para-position carbon atom of a phenolic hydroxyl group is held on a base material. The anti-cedar pollen allergen member.
The gist of the invention described in claim 6 is that a lignocellulosic material is prepared by adding an acid to a lignocellulosic material in which the number of phenolic hydroxyl groups of a phenol derivative is 2 and 1, and mixing and mixing them. While dissolving or swelling the carbohydrate in the acid, the lignin in the lignocellulosic material is reacted with the phenol derivative to obtain a phenol derivative having 2 phenolic hydroxyl groups and a phenol derivative having 1 phenolic hydroxyl group. It exists in the manufacturing method of the anti- cedar pollen allergen composition which obtains the anti- cedar pollen allergen composition of the lignophenol derivative synthesize | combined by mixing.

An anti-cedar pollen allergen composition containing at least a phenol derivative having 2 phenolic hydroxyl groups and containing a lignophenol derivative, or an anti-cedar pollen allergen member having the base material held thereon, as in claims 1 and 4 As a result, among the lignophenol derivatives, the lignophenol derivative having 2 phenolic hydroxyl groups has a remarkable effect on the reduction of cedar pollen allergen. If the phenol derivative is catechol or resorcinol as in claim 2, a more remarkable effect is obtained. In addition, since the lignophenol derivative uses plant-derived lignin as a raw material, it becomes an anti-cedar pollen allergen composition and an anti-cedar pollen allergen member excellent in safety.
As in Claims 3 and 6, a lignocellulosic material in which a phenol derivative having 2 phenolic hydroxyl groups and a phenol derivative having 1 phenolic hydroxyl group are mixed and sorbed is mixed with an acid and synthesized. The lignophenol derivative anti-cedar pollen allergen composition improves productivity by mixing a phenol derivative having 1 phenolic hydroxyl group, and the phenol derivative having 1 phenolic hydroxyl group is a phenolic hydroxyl group. Therefore, the anti-cedar pollen allergen composition is economically superior. Nevertheless, it has a high effect on reducing cedar pollen allergens and is extremely beneficial.

  The anti-cedar pollen allergen composition, the production method thereof, and the anti-cedar pollen allergen member of the present invention not only exhibit excellent effects in reducing cedar pollen allergens, but also are excellent in safety and more efficiently and inexpensively provided. It has a great effect such as being economical and excellent.

  In the process of studying the anti-cedar pollen allergen composition, the present inventors paid attention to ligno polyphenol among lignin phenol derivatives with promising cedar pollen allergen reduction, but according to the conventional method for producing lignophenol derivatives, We faced a situation where the yield dropped significantly as the amount of phenolic hydroxyl group introduced into lignin increased. The conventional production method is a third method described in JP-A No. 2001-261839 as shown in FIG. 7 (hereinafter referred to as “two-step process II”), and sorbs a phenol derivative onto a lignocellulosic material ( “Phenol derivative sorption process”). An acid capable of dissolving or swelling cellulose is added to the lignocellulosic material and stirred vigorously. After reacting for a predetermined time, it is poured into water to stop the reaction (“acid reaction step”). It is obtained by separating the carbohydrate fraction and lignophenol derivative fraction by solid-liquid separation such as centrifugation and filtration, and repeatedly washing with a large amount of water until the vicinity of neutralization in order to remove residual acid and carbohydrate from the latter. The insoluble fraction, that is, the water-washed neutralized lignophenol derivative is thoroughly dried (“water-washing neutralization step”). Then, for the purpose of separating carbohydrates and lignophenol derivatives contained in the water-washed neutralized lignophenol derivative, it is dissolved and recovered in a lignophenol derivative parent solvent such as acetone, which is soluble only in the latter (“extraction process”). Thereafter, in order to remove the low molecular weight lignophenol derivative having low molecular weight and the unreacted phenol derivative, the lignophenol derivative solution is dropped into a lignophenol derivative poor solvent such as diethyl ether to uniformize the molecular weight to some extent ( “Purification step”).

  Here, when polyhydric phenol is used in the sorption step, the affinity between the lignophenol derivative and water increases in the water washing neutralization step as the amount of phenol hydroxyl increases, so solid-liquid separation (centrifugation, filtration) And the like, and the yield of lignophenol derivatives is significantly reduced. As a method for solving this problem, JP-A-2001-342353 discloses a method using 95% phosphoric acid having a lower acid strength than sulfuric acid, but the cost is higher than that of sulfuric acid and the reaction requires heating. There was a problem that there was. In addition, polyhydric phenols are more expensive than monohydric phenols, and there is a problem that the production cost of lignophenol itself increases.

  The present inventors have conducted research and found that the cedar pollen allergen is unique unlike the mite allergen, and even in the phenol derivatives, the lignophenol derivative having 2 phenolic hydroxyl groups has a remarkable effect. It was. At the same time, diligent research has been conducted to solve the above problems, and the production of lignophenol derivatives having 2 phenolic hydroxyl groups in the phenol derivatives is difficult in low yields, and dihydric phenols are expensive. In view of the above, a method for producing a lignophenol derivative using a lignocellulosic material in which a phenol derivative having two phenolic hydroxyl groups and a low-cost phenol or the like is mixed and sorbed in some cases Tried to see if is valid. A lignophenol derivative using a phenol derivative having 2 phenolic hydroxyl groups, a phenol derivative having 2 phenolic hydroxyl groups, wherein the phenol derivative is introduced into lignin, and The present inventors found that a lignophenol derivative synthesized by mixing a phenol derivative having 2 phenolic hydroxyl groups with a phenol derivative having 1 phenolic hydroxyl group effectively acts to reduce cedar pollen allergen. .

Hereinafter, an embodiment of an anti-cedar pollen allergen composition, a method for producing the same, and an anti-cedar pollen allergen member according to the present invention will be described in detail.
(1) Anti-cedar pollen allergen composition The anti-cedar pollen allergen composition of the present invention, as described in JP-A-2001-261839, permeates a lignocellulosic material such as wood powder with a solvent in which a phenol derivative is dissolved. Then, the solvent is distilled off (the phenol derivative sorption step), and then the lignocellulosic material is mixed with an acid to dissolve the carbohydrate in the acid, while the ortho position of the phenolic hydroxyl group of the phenol derivative and / or A lignophenol derivative having a 1,1-bisarylpropane unit in which a carbon atom at the para position is bonded to a carbon atom at the C1 position of the arylpropane unit of lignin (FIG. 1), and the number of phenolic hydroxyl groups of the phenol derivative It contains a lignophenol derivative having a value of 2. A lignophenol derivative in which the number of phenolic hydroxyl groups of the phenol derivative is 2, among the lignophenol derivatives, exhibits an outstanding effect in reducing the anti-cedar pollen allergen. In particular, a lignophenol derivative obtained by reacting and synthesizing the above phenol derivative with catechol or resorcinol exhibits a remarkable effect as an anti-cedar pollen allergen composition.

The lignophenol derivative is, for example, a crude lignophenol derivative in an insoluble section separated by adding water after adding an acid to a lignocellulosic material sorbed with a phenol derivative as described in JP-A-2001-131201, Alternatively, of the crude lignophenol derivative, a lignophenol derivative extract dissolved in a lignophenol parent solvent (for example, acetone or methanol), and further the lignophenol derivative extract is dropped into a large excess of a poor solvent (for example, diethyl ether or isopropyl ether). The refined lignophenol derivative obtained by doing. The total amount of phenol derivative to be sorbed is not particularly limited, but 1 mol / C9 or more is desirable for effective grafting to natural lignin. The parent solvent means a solvent in which carbohydrates are hardly soluble and lignophenol derivatives and phenol derivatives are easily soluble, and the poor solvent is a solvent in which lignophenol derivatives are hardly soluble and excess (unreacted) phenol derivatives are soluble. Say. The lignophenol derivatives referred to in the present invention include JP 2004-210899, JP 2004-137347, JP 2004-115736, JP 2003-268116, JP 2001-261839, JP 2001-131201, JP 2003-131. 181863, JP-A-2001-64494, JP-A-2001-34233, JP-A-9-278904, JP-A-2-23701, and other known lignophenol derivatives, crude lignophenol derivatives, purified lignophenol derivatives, lignin Phenol derivatives are included.
The lignocellulosic material is a plant such as softwood or hardwood containing lignin and cellulose. For example, wood, wood powder, woody material such as plywood, laminated wood, particle board, newspaper, cardboard, and the like, and waste materials thereof. Also applicable are various herbaceous plants such as kenaf, bagasse, bamboo, straw, EFB, and agricultural waste. The acid is an acid that swells with respect to cellulose. 65% by weight or more of sulfuric acid (for example, 72% sulfuric acid), 85% or more of phosphoric acid, 38% or more of hydrochloric acid, p-toluenesulfonic acid, trifluoroacetic acid , Trichloroacetic acid, formic acid and the like.

  Further, in the step of sorbing the phenol derivative onto the lignocellulosic material in the “phenol derivative sorption step”, the phenol derivative having 2 phenolic hydroxyl groups (hereinafter referred to as “divalent phenol”) When a phenol derivative having 1 phenolic hydroxyl group (hereinafter referred to as “monohydric phenol”) is mixed and sorbed at a predetermined ratio, it is more preferable from the viewpoint of performance, cost, and the like. While an acid is added to and mixed with a lignocellulosic material in which the number of phenolic hydroxyl groups of the phenol derivative is 2 and 1, the carbohydrate in the lignocellulosic material is dissolved or swollen in the acid. , By reacting the lignin in the lignocellulosic material with the phenol derivative, the phenol derivative having two phenolic hydroxyl groups is mixed with one, and the carbon atom at the C1 position of the arylpropane unit of lignin is mixed. And an anti-cedar pollen allergen composition containing a lignophenol derivative having a 1,1-bisarylpropane unit to which the ortho-position and / or para-position carbon atom of the phenolic hydroxyl group related to the phenol derivative is bonded. (Figure 2). It can contribute to reduction of cedar pollen allergen and cost reduction of anti-cedar pollen allergen composition. The dihydric phenol is very reactive with the monohydric phenol and functions as an anti-cedar pollen allergen with a small amount of the dihydric phenol relative to the monohydric phenol. The ratio when sorbed to the lignocellulosic material is effective in reducing cedar pollen allergens in the range of dihydric phenol / monohydric phenol = 0.01 to 9.9. The lower limit is set to 0.01 because if the amount of dihydric phenol is less than this, the anti-cedar pollen allergen function of ligno dihydric phenol will not be exhibited. On the other hand, if the amount is larger than the upper limit value 9.9, there is a problem that the solid-liquid separation property in the water washing neutralization process is not improved. More preferably, it is the range of 0.05-1.0. Within this range, a lignophenol derivative-containing compound that exhibits an anti-cedar pollen allergen effect can be easily obtained in high yield, and the amount of expensive dihydric phenol used can be reduced.

  The dihydric phenol and monohydric phenol are not limited to one type each. Divalent phenols, that is, phenol derivatives having 2 phenolic hydroxyl groups, include catechol, alkylcatechol, resorcinol, alkylresorcinol, hydroquinone, alkylhydroquinone and the like. Monovalent phenols, that is, phenol derivatives having one phenolic hydroxyl group, include phenol and p-cresol. In addition, the kind of substituent which a phenol derivative may have is not limited.

(2) Method for producing anti-cedar pollen allergen composition The method for producing an anti-cedar pollen allergen composition is, for example, adding an acid to a lignocellulosic material in which a phenol derivative containing a dihydric phenol is sorbed, and mixing. After the carbohydrate in the lignocellulosic material is dissolved or swollen in an acid and the lignin in the lignocellulosic material is reacted with a phenol derivative, the reaction is stopped by adding water to the mixed solution. The insoluble fraction separated from the phase is recovered, and then the insoluble fraction is washed with water and solid-liquid separated, and the lignophenol derivative anti-cedar pollen allergen composition is obtained from the water-insoluble fraction that is insoluble in water. . When catechol or resorcinol is used as the phenol derivative of the dihydric phenol, an anti-cedar pollen allergen composition that is more effective than the cedar pollen allergen can be obtained.

  In addition, an acid is added to and mixed with a lignocellulosic material in which the number of phenolic hydroxyl groups of the phenol derivative is 2 and 1, and the carbohydrates in the lignocellulosic material are dissolved or swollen in the acid. On the other hand, a lignophenol derivative synthesized by reacting lignin in a lignocellulosic material with the phenol derivative and mixing a phenol derivative having 2 phenolic hydroxyl groups and a phenol derivative having 1 phenolic hydroxyl group. An anti-cedar pollen allergen composition can be produced. Such a production method is more preferable because an anti-cedar pollen allergen composition can be obtained at low cost. Specifically, a solvent (for example, acetone or ethanol) in which a phenol derivative having 2 phenolic hydroxyl groups and a phenol derivative having 1 phenolic hydroxyl group are mixed and dissolved is infiltrated into the lignocellulosic material. The solvent is distilled off (phenol derivative sorption step). Next, an acid is added to and mixed with the sorbed lignocellulosic material, and the mixed solution is obtained by dissolving or swelling the carbohydrate in the lignocellulosic material in the acid and reacting the lignin in the lignocellulosic material with the phenol derivative. After that, the reaction was stopped by adding water to the mixed solution, and the insoluble section phase-separated from the acid phase was recovered (acid reaction step) .Then, the insoluble section was washed with water and solid-liquid separated to be insoluble in water. Lignophenol derivatives are obtained from the water-insoluble sections. Then, the obtained water-insoluble section, that is, water-washed neutralized lignophenol derivative is dried (“water-washed neutralization step”). An anti-cedar pollen allergen composition of a lignophenol derivative synthesized by mixing a phenol derivative having 2 phenolic hydroxyl groups and a phenol derivative having 1 phenolic hydroxyl group is produced (FIG. 2). By mixing inexpensive monohydric phenol with expensive dihydric phenol, the cost of the anti-cedar pollen allergen composition product can be reduced. It is possible to maintain the outstanding cedar pollen allergen reduction effect possessed by the lignophenol derivative of phenol. Furthermore, the production of lignophenol derivatives is facilitated and contributes to the improvement of productivity.

(3) Anti-cedar pollen allergen member The above-mentioned anti-cedar pollen allergen composition can be powdered and directly sucked into a vacuum cleaner, dust collector, etc., and used as it is, but is usually held on a substrate or liquid carrier as a solid carrier. Used. The content of the lignophenol derivative in the anti-cedar pollen allergen composition is usually 0.01 to 50% by weight, more preferably 1 to 30% by weight, and the anti-cedar pollen allergen composition is provided. Is done. The use form of the anti-cedar pollen allergen composition and the anti-cedar pollen allergen substance of the present invention is any form such as liquid, powder, paste, etc., as long as the treatment can inactivate the cedar pollen allergen in the environment. Can also be taken. From the viewpoint of handling, it is easy and effective to make it liquid. Solvents necessary for uniformly dispersing these reducing substances can be used alone or as a mixed solvent. The kind of solvent is not specifically limited. An anti-cedar pollen allergen composition containing the lignophenol derivative such as resorcinol is appropriately dissolved in an alkali, water, acetone, or alcohol and held on a substrate such as a filter made of nonwoven fabric. The method of holding the anti-cedar pollen allergen composition on a substrate such as a filter made of nonwoven fabric is not limited to impregnation or dripping, and any method may be used. For example, it has been confirmed that the anti-cedar pollen allergen composition is continuously effective for reducing the anti-cedar pollen allergen by impregnating and holding the anti-cedar pollen allergen composition in a woven fabric mask as a base material. The effect of reducing the anti-cedar pollen allergen can be increased by appropriately selecting the type of solution for dissolving these anti-cedar pollen allergen compositions and the material of the nonwoven fabric as the base material.

  In addition, the anti-cedar pollen allergen composition of the present invention may be used alone or in combination with other materials to form paints and coating agents having an allergen-reducing effect, and resin molded products such as window frames, blinds, and screen doors. Can do. Other office supplies such as desks, chairs, shelves, partitions, etc., household items such as tables, chairs, sheets, beds, tableware, lighting fixtures, storage furniture such as baskets, housing structures such as frames, and tatami core materials The anti-cedar of the present invention is applied to each of these base materials (articles) constituting all living spaces such as core materials, flooring, coating agents for coating floor materials, stairs, housing-related facilities such as members around windows, etc. The pollen allergen composition can be used alone or in combination with other ingredients to obtain a product (anti-cedar pollen allergen member) having a cedar pollen allergen reducing effect.

1. Method of synthesizing lignophenol derivatives 50 g of acetone-defatted cedar wood flour was added to 400 ml of an acetone solution in which each of the phenol derivatives in the prescribed amounts shown in Table 1 was dissolved so that the amount was twice the molar amount per C-9 unit. Soaked overnight. Sorpted wood flour was prepared by drying under reduced pressure until the acetone was completely distilled off using a rotary evaporator.

Sorpted wood flour was weighed so that the weight of the absolute dry wood flour was 10 g, 30 ml of 72% sulfuric acid was added, and the mixture was stirred for 15 minutes, 20 minutes or 60 minutes. Thereafter, the reaction was stopped by diluting with 60 ml of deionized water. After the reaction was stopped, suction filtration was performed using a polypropylene filter (flat membrane, diameter 47 mm), and solid-liquid separation was performed. The cake obtained by filtration was dispersed in 700 ml of deionized water, centrifuged (4000 G, 10 minutes), and the supernatant was removed. Again, the precipitate was dispersed in deionized water and then centrifuged to remove the supernatant. This operation was repeated until the supernatant became neutral. After washing to neutrality, the precipitate was immediately frozen, and a powder (hereinafter referred to as “crude lignophenol derivative”) was obtained by lyophilization. 1 g of the obtained crude lignophenol derivative was extracted with 50 ml of acetone, methanol or 80% aqueous methanol, and after centrifugation (2500 G, 15 minutes), the supernatant was concentrated and lyophilized. For lignocresol, the acetone extract from the crude lignophenol derivative was further added dropwise to a large excess of diethyl ether, and the precipitate was dried under reduced pressure. The obtained precipitate was used as purified lignocresol.
Table 2 shows the yield and extract yield of the crude lignophenol derivative obtained.

  The yield of crude lignophenol derivative extract was in the order of cresol> catechol (20 minutes)> catechol (60 minutes)> pyrogallol (20 minutes)> resorcinol (20 minutes)> resorcinol (60 minutes)> pyrogallol (60 minutes) became. In the synthesis of lignopolyphenol, the yield is reduced compared to monohydric phenol due to oxidation in the acid treatment step and the drying step. Since pyrogallol has three phenolic hydroxyl groups in one molecule, the water solubility of the product increases with the extension of the acid treatment time, and most of it flows out in the water washing neutralization process, so the crude lignophenol derivative The yield of is significantly reduced. Since resorcinol is more reactive than catechol and pyrogallol, it is thought that condensation occurs simultaneously with oxidation in the acid treatment step, making it difficult to extract and the yield of the extract is reduced.

2. Reduction test of cedar pollen allergen and mite allergen
The lignophenol derivatives and commercially available tannins synthesized in 1 above (sun flavone manufactured by Taiyo Kagaku Co., Ltd., Watlu tannin, chestnut tannin, tannic acid manufactured by Kawamura Tsusho Co., Ltd.) j1) A reduction test was conducted. Filter paper (2 cm x 2 cm, ADVANTEC 5A) is impregnated with 100 μl of each sample solution dissolved in distilled water, acetone, methanol, or 80% aqueous methanol solution to the specified concentration (5%, 3%, 2%, w / v). I let you. A sample-impregnated filter paper that has been thoroughly air-dried is cut into 1 cm x 1 cm, and 1 ml of phosphate buffer (pH 7.4) containing 30 ng / ml or 200 ng / ml of each antigen (Der f1, Cry j1, Seikagaku Corporation) Soaked in water, shaken for 100 minutes, and allowed to stand overnight. After centrifugation, the antigen concentration remaining in the supernatant was measured by ELISA using a tick Der f1 and cedar pollen Cry j1 measurement kit (manufactured by LCD Allergy Laboratory Co., Ltd.). The results are shown in FIGS. Abbreviations in the figure are as described in Table 3.

  For Der f1, the 80% methanol water extract of ligno polyphenols showed a high reduction effect. For lignopyrogallol, a high effect was confirmed even with a crude lignophenol derivative. Commercially available tannins were confirmed to be highly effective except for sun flavones, which are green tea extracts. Sun flavone is considered to have a relatively low effect because it contains a large amount of low molecular weight tannin compared to other commercially available tannins. Among the hydrolyzed tannins, tannins of any kind were confirmed because they were highly effective in chestnut tannin composed of ellagitannin, tannic acid composed of gallotannin, and wattle tannin composed of condensed tannin. It was revealed that Der f1 has a high reduction effect.

On the other hand, for Cry j1, a high effect was confirmed only for the lignocatechol 80% methanol extract and lignoresorcinol 80% methanol extract as shown in FIG. For lignoresorcinol, the effect was confirmed even with crude lignophenol derivatives. Tannins had only a slight effect on hydrolyzed tannins, chestnut tannin and tannic acid.
The allergen-reducing mechanism of tannins and lignophenol derivatives is thought to involve high affinity for proteins. From this, it is expected that a composition having an effect on Der f1 will show the same high effect on other allergens, but the results were different.
The interaction (adsorption) of tannin and protein is greatly affected by the conformation of each protein, and hydrogen bonds and hydrophobic amino acids generated between the carbonyl oxygen of the peptide bond appearing on the protein surface and the phenolic hydroxyl group of tannin. Proteins are denatured by hydrophobic bonds. However, the antigenicity of Cry j1, which is a glycoprotein, is thought to involve a large portion of the sugar chain rather than the peptide chain. Therefore, lignoresorcinol and lignocatechol having 2 phenolic hydroxyl groups act specifically on this sugar chain part, and thus are not seen in tannins and lignopyrogallol having 3 phenolic hydroxyl groups. It is thought that was demonstrated.

3. Method for synthesizing lignophenol-resorcinol Lignoresorcinol showed a high reduction effect on Cry j1, but as mentioned above, the yield is the lowest among the lignophenols, so efficient production of lignoresorcinol. The method was examined.
50 g of acetone-degreased cedar wood flour was immersed overnight in 400 ml of an acetone solution in which a predetermined amount of phenol and resorcinol shown in Table 4 were dissolved so that the total amount per C-9 unit was 2 times the molar amount. Sorpted wood flour was prepared by drying under reduced pressure until the acetone was completely distilled off using a rotary evaporator.

A lignophenol derivative was synthesized from the prepared sorption wood flour in the same manner as in 1. After the acid treatment step, the filtrate obtained by suction filtration was diluted 400 times and the amount of sugar contained was quantified by the phenol / sulfuric acid method. That is, 250 μl of a 7% phenol aqueous solution was added to 250 μl of the diluted sample solution and mixed well, and 2.5 ml of concentrated sulfuric acid was added thereto and mixed. After cooling in a water bath, the absorbance at a wavelength of 480 nm was measured after 20 minutes. The total amount of sugar was calculated from a calibration curve prepared with glucose, and the carbohydrate degradation rate was determined by the following formula.
Carbohydrate decomposition rate (%) = {total sugar amount in filtrate (g / ml)} / 0.081 (g / ml) ^* × 100
* A pentose of 0.081g / ml {0.081g / ml = (wood flour 10g × 0.73) / 90ml} is detected in the filtrate after hydrolysis, assuming that 73% of carbohydrates are contained in the cedar wood Assumed.
Table 5 shows the filterability, yield and carbohydrate decomposition rate of each crude lignophenol derivative during deoxidation.

When wood powder sorbed with resorcinol alone was acid-treated, the acid treatment for 20 minutes could complete the filtration in 26 minutes, but the cake 4 cm and the cake were not sufficiently dehydrated. The filter was clogged after 60 minutes of acid treatment and could not be filtered. The wood powder sorbed only with phenol had good filterability, and the filtration was completed in about 2 minutes. When phenol and resorcinol were mixed and sorbed at a ratio of 3: 1, resorcinol alone was improved in filterability by 60 minutes, but filtration could not be completed. When 9: 1 mixed phenol and resorcinol were mixed, the filterability was very good and the filtration was completed in 2 minutes and 50 seconds, although it was slightly inferior to the case of phenol alone. From this fact, it was clarified that productivity is greatly improved by mixing and sorption of phenol and polyhydric phenol in the sorption step. When phenol and resorcinol were set to 3: 1, filtration with this suction filtration could not be completed completely, but the filterability was clearly improved, and solid-liquid separation methods such as pressure filtration and filter press in the future. Then, it can be said that it is sufficiently separable. Moreover, the separability by centrifugation was better than that of resorcinol alone, and the solid-liquid separability was improved comprehensively by mixing with phenol. Furthermore, when the yield of the crude lignophenol derivative was compared, the yield was improved by mixing and sorption of phenol. The 20-minute treatment with resorcinol alone has a high crude lignophenol derivative yield of 56.9%, which is thought to be due to the low carbohydrate degradation rate. Actually, the carbohydrate degradation rate is about one-third of the 60-minute treatment, and it is considered that all unreacted carbohydrate is contained in the crude lignin.
Table 6 shows the extraction rate of each lignophenol derivative.

  By mixing and sorption of phenol and resorcinol, the extraction efficiency was improved for any solvent compared to resorcinol alone. For each of the synthesized lignophenol derivatives and extracts thereof, the allergen reducing effect was confirmed by the same method as in 2. The results are shown in FIGS. Abbreviations in the figure are as described in Table 7. Note that the antigen concentration in FIG. 6 is 30 ng / ml, whereas the antigen concentration in FIG. 4 is 200 ng / ml. In the ELISA method using the cedar pollen Cry j1 measurement kit, the Cry j1 reduction rate tends to decrease as the antigen concentration decreases. FIG. 6 shows that the Cry j1 reduction rate is lower than in FIG. It shows a low value in general.

For Der f1, the effect decreased as the proportion of resorcinol sorbed during the synthesis of the lignophenol derivative decreased, but a certain effect was confirmed.
On the other hand, Cry j1 showed a high effect even when phenol: resorcinol = 9: 1. Furthermore, in the case of resorcinol alone, the effect of the crude lignophenol derivative was low, but in the case of phenol: resorcinol = 9: 1, the effect of the crude lignophenol derivative was high, and from the arithmetic average value in the case of phenol alone and resorcinol alone Was also highly effective. This is thought to be because not only the number of phenolic hydroxyl groups simply increased, but also the conformation in which phenol and resorcinol were introduced into lignin at the same time, and thus it was easy to show affinity with Cry j1.
Therefore, by mixing not only dihydric phenol but also monohydric phenol as the sorbed phenol derivative at the time of synthesizing lignophenol derivative, lignophenol derivative showing high effect in reducing cedar pollen allergen can be obtained efficiently and in high yield. It can be said that it is possible.

  The present invention is not limited to those shown in the above-described embodiments and examples, and various modifications can be made within the scope of the present invention depending on the purpose and application.

It is a grafting figure of the phenol derivative to natural lignin C1. It is an introduction grafting figure of the mixed phenol derivative to natural lignin. It is a measurement figure showing the mite allergen reduction effect of a lignophenol derivative and tannins. It is a measurement figure showing the cedar pollen allergen reduction effect of a lignophenol derivative and tannins. It is a measurement figure showing the mite allergen reduction effect of various lignophenol derivatives. It is a measurement figure showing the cedar pollen allergen reduction effect of various lignophenol derivatives. It is a flowchart of the conventional manufacturing process “two-stage process II”.

Claims (6)

It contains at least a phenol derivative having 2 phenolic hydroxyl groups, and the carbon atom at the C1 position of the arylpropane unit of lignin is bonded to the carbon atom at the ortho position and / or the para position of the phenolic hydroxyl group related to the phenol derivative. An anti-cedar pollen allergen composition comprising a lignophenol derivative having a 1,1-bisarylpropane unit. The anti-cedar pollen allergen composition according to claim 1, wherein the phenol derivative is catechol or resorcinol. A phenol derivative having 2 and 1 phenolic hydroxyl groups is mixed, and the ortho-position and / or para-position of the phenolic hydroxyl group of the phenol derivative is added to the carbon atom at the C1 position of the arylpropane unit of lignin. An anti-cedar pollen allergen composition comprising a lignophenol derivative having a 1,1-bisarylpropane unit having carbon atoms bonded thereto. 1,1 in which the number of phenolic hydroxyl groups of the phenol derivative is 2, and the carbon atom at the C1 position of the arylpropane unit of lignin is bonded to the carbon atom at the ortho and / or para position of the phenolic hydroxyl group according to the phenol derivative. -An anti-cedar pollen allergen member comprising a base material and an anti-cedar pollen allergen composition containing a lignophenol derivative having a bisarylpropane unit. A phenol derivative having 2 and 1 phenolic hydroxyl groups is mixed, and the ortho-position and / or para-position of the phenolic hydroxyl group of the phenol derivative is added to the carbon atom at the C1 position of the arylpropane unit of lignin. An anti-cedar pollen allergen member comprising a base material and a lignophenol derivative-containing anti-cedar pollen allergen composition having a 1,1-bisarylpropane unit to which a carbon atom of 1 is bonded. While an acid is added to and mixed with a lignocellulosic material in which the number of phenolic hydroxyl groups of the phenol derivative is 2 and 1, the carbohydrate in the lignocellulosic material is dissolved or swollen in the acid. The anti-lignophenol derivative is synthesized by reacting lignin in a lignocellulosic material with the phenol derivative and mixing a phenol derivative having 2 phenolic hydroxyl groups and a phenol derivative having 1 phenolic hydroxyl group. A method for producing an anti-cedar pollen allergen composition to obtain a cedar pollen allergen composition.

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