JP4845516B2 - Water resistance method for catechins - Google Patents

Description

The present invention is selected from catechins having a weight ratio A / B of gallate catechin (A) and non-gallate catechin (B) of 0.8 or more, water-soluble cellulose ethers, polyalkyl ethers and polyvinyl alcohols. The present invention relates to a water resistance method for catechins, which comprises mixing and reacting one or more water-soluble polymer compounds.

Catechins are known to have functions such as deodorant properties, antibacterial properties, and antiviral properties. Taking advantage of these functions, for example, antifungal antibacterial antiviral filters (Patent Document 1), sheets, It is used as a functional component in various architectural and furniture materials such as films and foams, and filters.
However, since catechins are water-soluble, if the formed product such as a filter coated with an aqueous solution of catechins is washed with water, the applied catechins are eluted and the antibacterial and deodorizing properties are greatly reduced. End up. Further, when catechins are supported on a formed product such as a sheet, they are eluted in a high humidity environment, and there are problems such as color transfer. For this reason, a technique for imparting water resistance to catechins has been strongly demanded.

Known water resistance methods for catechins include a method in which a functional component such as catechin and a ceramic component are blended in a resin and melt-molded (Patent Document 2), and a tea extract is porous such as silica. Examples thereof include a method (Patent Document 3) in which fine particles are contained and chelated with a metal salt solution to form a water-insolubilized product. However, the method of blending a functional component such as catechin and a ceramic component into a resin and melt-molding it can be used only for a molded product made of resin, and generally catechins embedded in a resin are desired. It is thought that the function of can not be demonstrated. In addition, the method of containing a tea extract in porous fine particles and chelating with a metal salt solution to make a water insolubilized product has problems of coloring and harmfulness to the human body, and the functional group of catechins is a metal chelate. Therefore, the functions of catechins may not be retained. Furthermore, these methods require the installation of dedicated equipment, and it has been difficult to use existing equipment easily.

Other methods for making water resistant to catechins include a method in which polyphenols are polymerized with aldehydes to make them hardly soluble in water (Patent Document 4). However, this method is not preferable in that aldehydes, which are harmful air pollutants, are used as auxiliary materials, and it is considered that the aldehyde removal function of catechins is not exhibited because they react with aldehydes for polymerization. Here, as a method for making polyphenols poorly soluble, there is a method in which high-molecular polyphenols such as tannic acid are hardly solubilized and precipitated with methylcellulose, which is a water-soluble polymer compound, and is used for removing tannins (non-patent literature). 1). However, low molecular weight polyphenols such as catechin have been difficult to form hardly soluble precipitates with methylcellulose (Non-patent Document 1).
JP-A-10-315 JP 2000-204277 A JP 2002-060309 A JP 2003-176329 A Journal of Japanese Society of Food Industry Vol.18 No.1 (1971) p. 28-32

An object of the present invention is to provide a water resistance method for catechins that overcomes the above problems and is excellent in workability and safety, a water resistant product of catechins that retains the function of catechins, and a water resistant fixed formed product of catechins. That is.

As a result of intensive studies to achieve the above object, the present inventors have found that when the ratio of gallate catechins to non-gallate catechins in catechins, which are low-molecular polyphenols, is specific, water-soluble cellulose ethers, It has been found that water resistance is achieved by water-soluble polymer compounds such as alkyl ethers and polyvinyl alcohols, and the present invention has been completed.
That is, the present invention according to claim 1 is directed to catechins having a weight ratio A / B of gallate catechin (A) and non-gallate catechin (B) of 0.8 or more, water-soluble cellulose ethers, polyalkyls It is a water resistance method for catechins characterized in that one or more water-soluble polymer compounds selected from ethers and polyvinyl alcohols are mixed and reacted.

Further, the present invention according to claim 2 is directed to catechins having a weight ratio A / B of gallate catechin (A) and non-gallate catechin (B) of 0.8 or more, water-soluble cellulose ethers, polyalkyls A water resistance-improving method for catechins, characterized in that one or more water-soluble polymer compounds selected from ethers and polyvinyl alcohols are mixed and reacted under acidic conditions.

Further, in the present invention according to claim 3, one or more water-soluble polymer compounds selected from water-soluble cellulose ethers, polyalkyl ethers and polyvinyl alcohols with respect to catechins are 0.5. The water resistance method according to claim 1 or 2, wherein the water resistance is -50 times weight.

The present invention according to claim 4 is characterized in that the water-soluble cellulose ether is one or more water-soluble polymer compounds selected from methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl methyl cellulose, and the polyalkyl ether is polyethylene. Water resistance according to any one of claims 1 to 3, which is one or more water-soluble polymer compounds selected from glycol, polypropylene glycol and trimethylolpropane polypropylene glycol ether, and the polyvinyl alcohol is polyvinyl alcohol. Is the method.

Further, the present invention according to claim 5 is a catechin water-resistant product obtained by the water resistance method according to any one of claims 1 to 4.

Moreover, this invention of Claim 6 contains the catechin water-resistant thing of Claim 5, It is a deodorizer characterized by the above-mentioned.

Moreover, this invention of Claim 7 contains the catechin water-resistant thing of Claim 5, It is a foodstuff or its raw material characterized by the above-mentioned.

The present invention according to claim 8 is a formed article characterized by supporting the catechin water-resistant product according to claim 5.

Further, the present invention according to claim 9 is a catechin water-resistant immobilization formed product, wherein the catechin is water-immobilized to the formed product using the water resistance method according to any one of claims 1 to 4. It is.

The invention according to claim 10 is the catechin water-resistant immobilization formed product according to claim 9, characterized in that the formed product is fibers.

The invention according to claim 11 is the catechin water-resistant immobilization formed product according to claim 9, characterized in that the formed product is a wood material.

The invention according to claim 12 is the catechin water-resistant immobilization formed article according to claim 9, wherein the formed article is rubber.

The invention according to claim 13 is the catechin water-resistant immobilization formed product according to claim 9, characterized in that the formed product is a plastic.

Further, the present invention according to claim 14 is the catechin water-resistant immobilization formed article according to claim 9, characterized in that the formed article is a building / furniture material.

The invention according to claim 15 is the catechin water-resistant immobilization formed article according to claim 9, characterized in that the formed article is a sheet.

Moreover, this invention of Claim 16 is a catechin water-resistant fixed formation of Claim 9 characterized by the above-mentioned.

The water resistance method of the present invention does not need to go through complicated steps, and only reacts a catechin with a water-soluble polymer compound. Therefore, the water resistance method is excellent in safety and versatility, and the water resistance is supported on various materials. It is possible to dampen. The water-resistant catechins have water resistance, and various functions of the catechins are retained even in the water-resistant state. It also has an effect of suppressing the diffusion of bitter and astringent taste derived from catechins in the oral cavity. Furthermore, in the catechin water-resistant immobilization product in which catechins are water-immobilized to the formed product using the water resistance method of the present invention, elution of catechins due to washing or the like can be suppressed.

The present invention is described in detail below.
The catechins in the present invention are mainly made from tea leaves (Camellia sinensis), leaves, stems, and green tea, black tea, oolong tea, pear tea, etc., which are water, hot water, organic solvents, It is a component contained in a tea extract obtained by extraction with a water-containing organic solvent or the like, and non- (±) -catechin, (−)-epicatechin, (−)-epigallocatechin, (±) -gallocatechin, etc. It refers to a generic name for gallate catechins and gallate catechins such as (−)-epicatechin gallate, (−)-catechin gallate, (−)-epigallocatechin gallate, and (−)-gallocatechin gallate.

These catechins can be purified from the tea extract to a desired concentration by using an organic solvent fraction or an adsorbent resin. In the present invention, these refined products can be used singly or in appropriate combination of two or more, and can be used in the form of the above-mentioned tea extract which is a crude product.
As the tea extract, for example, it is easy to use commercially available products such as “Polyphenone” manufactured by Mitsui Norin Co., Ltd., “Sunphenon” manufactured by Taiyo Kagaku Co., Ltd., and “Tearfuran” manufactured by ITO EN Co., Ltd.

The water-soluble polymer compound used in the present invention is preferably one that exhibits reactivity with catechins, and examples thereof include water-soluble cellulose ethers, polyalkyl ethers, and polyvinyl alcohols. Selected. Examples of water-soluble cellulose ethers include, but are not limited to, methyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl methyl cellulose. Among water-soluble cellulose ethers, methylcellulose and hydroxypropylmethylcellulose are more preferable because they are recognized as food additives and have high safety.

Methyl cellulose is a water-soluble polymer compound obtained by methyl etherification of cellulose and has different properties depending on the degree of substitution of the methoxy group (—OCH ₃ ). In the present invention, the degree of substitution is soluble in cold water and easy to handle. Is preferably 25% to 35%. Moreover, although the aqueous solution generally shows high viscosity, the low-viscosity goods processed easily can also be used similarly.

On the other hand, hydroxypropylmethylcellulose is a water-soluble polymer compound in which cellulose is substituted with methoxy group and hydroxypropoxy group (—OCH ₂ CHOHCH ₃ ), and hydroxypropylmethylcellulose also has a methoxy group substitution degree of 25% to 35%. Is preferably used. Hydroxypropyl methylcellulose has a lower viscosity than methylcellulose, is easily soluble in warm water, and has a high solubility in alcohol solutions, so it is easier to handle than methylcellulose. Commercially available water-soluble cellulose ethers are sold by Shin-Etsu Chemical Co., Ltd., Matsumoto Yushi Seiyaku Co., Ltd. and others.

Polyvinyl alcohols include polyvinyl alcohol and its derivatives. Among the polyvinyl alcohols, polyvinyl alcohol is preferable because it has many hydroxyl groups. Polyvinyl alcohol is a vinyl resin obtained by polymerizing and saponifying vinyl acetate, and its properties differ depending on the degree of polymerization and saponification, and generally has a high degree of polymerization, low saponification and high viscosity. Show.

In the present invention, although there is no particular limitation, it is preferable from the viewpoint of ease of handling to use those having a polymerization degree of 1000 or more and a saponification degree of 70% or more. Polyvinyl alcohol is sold by Kuraray Co., Ltd. or Nippon Synthetic Chemical Industry Co., Ltd.

Polyalkyl ethers are polymers having an ether bond in the alkyl main chain. Polyethylene glycol, polypropylene glycol and derivatives thereof such as trimethylol propane polypropylene glycol ether are those that have reactivity with catechins. It is mentioned, but it is not limited to them. Among the polyalkyl ethers, polyethylene glycol is preferred because it has the highest reactivity with catechin.

Polyethylene glycol is obtained by polymerizing ethylene glycol, and the average molecular weight is not particularly limited, but 200 to 50000 is preferable. Polyethylene glycol is sold by Asahi Denka Kogyo Co., Ltd. and Nippon Oil & Fat Co., Ltd.

The water resistance reaction rate between catechins and water-soluble polymers in the present invention is high in gallate catechins among catechins, and the weight ratio of gallate catechins (A) and non-gallate catechins (B) in the catechins used. A / B is preferably 0.8 or more, more preferably 1.0 or more, still more preferably 1.2 or more, particularly preferably 1.5 or more, and most preferably 2.0 or more. In the present invention, there is no problem even if catechins containing no non-gallate substance are used.

Since the water resistance reaction between catechins and water-soluble polymer compounds is promoted under acidic conditions, by making the solution containing catechins and / or water-soluble polymer compounds acidic, the water resistance reaction of catechins can be further improved. Improvement is expected. For example, it is preferable to adjust the pH to 5 or less for a 1 wt% catechin solution.

Various acids can be used as the method of acidification. The various acids are not particularly limited. Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and carbonic acid. Examples of organic acids include ascorbic acid, malic acid, citric acid, acetic acid, lactic acid, oxalic acid, and succinic acid. Acid, tartaric acid, erythorbic acid, formic acid, propionic acid, butyric acid, fumaric acid, adipic acid, aspartic acid, glutamic acid, etc. Is preferred.

The amount of the water-soluble polymer compound added to the catechins is preferably 0.5 to 50 times the weight, more preferably 0.8 to 20 times the weight, still more preferably 1 to 10 times the weight, most preferably from the water-resistant reaction rate. Is 2 to 5 times the weight.

The water-resistant product of catechins in the present invention can be obtained by mixing and reacting catechins and a water-soluble polymer compound. Various functions of catechins are maintained even in the state of water-resistant catechins, and can be used as a water-resistant functional substance by applying processing according to the form of use such as pulverization and molding. Moreover, it has a property which is not soluble in various organic solvents as well as water.

A water-resistant product comprising methylcellulose and / or hydroxypropylmethylcellulose which is a food additive and catechins which are natural products can also be used for food. For example, by using it as a coating agent such as a tablet serving as a health functional food, it is possible to mask the unpleasant taste or to delay the solubility of the tablet and make it enteric.

In addition, catechin water-resistant products obtained with methylcellulose and / or hydroxypropylmethylcellulose also have an effect of suppressing the diffusion of bitterness and astringency derived from catechins in the oral cavity, and are used as various edible compositions or raw materials thereof. It is possible.

The catechin water-resistant immobilization formed product in the present invention means a product obtained by immobilizing catechins having water resistance to a formed product by reacting catechins with a water-soluble polymer compound on the formed product.

Forms are classified according to their use, such as building / furniture materials, sheets, filters, etc., and those classified according to the materials include fibers, woody materials, rubbers, plastics, etc. There is.

Examples of fibers include chemical fibers such as synthetic fibers, regenerated fibers, semi-synthetic fibers, and inorganic fibers, natural fibers such as plant fibers and animal fibers, and clothing, curtains, carpets, and woven fabrics made from these raw materials. There are cloth, paper and mask.

Wood materials include lumber, short board, laminate, laminated wood, plywood, decorative plywood, particle board, fiber board, chip board, strand board, wood pulp, panel, paper, wood wool, charcoal, and processing them There are furniture, joinery, craft products, etc., regardless of the type of wood.

Rubbers include neoprene rubber, polybutadiene rubber, chloroprene rubber, styrene rubber, silicone rubber, fluorine rubber, acrylic rubber, butyl rubber, nitrile rubber, urethane rubber and other synthetic rubber, natural rubber, synthetic rubber latex, natural rubber latex, and These processed products are examples.

Plastics include thermoplastic resins such as polyethylene, polypropylene, styrene resin, AS resin, ABS resin, acrylic resin, TPS resin, polycarbonate, nylon, and heat such as melamine resin, phenol resin, urethane resin, and unsaturated polyester resin. These include curable resins, and include processed products such as paints and adhesives, molding materials, packaging materials, sundries, household items, and daily necessities made from these powders and pellets.

In addition to the processed products described above, there are gypsum boards, cement, tiles, tiles, glass, heat insulating materials, etc., as materials for construction and furniture, and any material may be used.

Sheets are formed products that are processed into paper, thin plates, or thin curtains, and examples include tatami mats, ridges, films, sheets, water-absorbing sheets, wallpaper, and bran paper.

The filter means an air cleaner, a humidifier, a ventilation fan, an air conditioner, a vacuum cleaner, a dust collector, etc. used in a non-woven dust collecting filter or a hepa filter for filtering and purifying gas or liquid.

The water-soluble polymer compound in the present invention has a property of insoluble dispersion when mixed in an organic solvent. In this state, even when catechins are added, a water-resistant product is not generated, and the dispersion system solution is maintained. In the case of a water-containing organic solvent, a hydrated product is produced from the contained water as the concentration of the organic solvent is reduced by a process such as drying.

Utilizing this phenomenon, a water-soluble polymer compound is dispersed in a water-containing organic solvent such as alcohol showing hydrophilicity, catechins are added and mixed uniformly, and then the mixed solution is applied to the formed product and further dried. Thus, it is possible to easily obtain a catechin water-resistant immobilization formed product through a step of generating a catechin water-resistant product while removing the solvent. Using this method, catechins and water-soluble polymer compounds can be uniformly supported in one step, and the production of catechins with water-resistant immobilization can be performed without greatly changing existing facilities and processes. It becomes possible.

Generally, the organic solvent concentration is preferably 30% by volume or more from the viewpoint of stability. The higher the solubility of the water-soluble polymer compound used in the organic solvent, the higher the concentration of the organic solvent in the mixed solution is preferred, and the higher the concentration of the water-soluble polymer compound in the mixed solution, the lower the concentration of the organic solvent. Keep the dispersion system stable.

The concentration of the water-soluble polymer compound and the catechins in the mixed solution is preferably 0.01% to 20% from the viewpoint of workability and stability. A solution obtained by mixing a water-soluble polymer compound and catechins in a water-containing organic solvent is very stable and can be stored in a mixed solution state, and can be distributed in this state.

The following examples further illustrate the present invention. However, the present invention is not limited to this. The catechin content was measured by the following method.

≪Measurement conditions for catechin content≫
The catechin content is determined using the HPLC method under the following conditions: (±) -catechin, (−)-epicatechin, (−)-epigallocatechin, (±) -gallocatechin, (−)-epicatechin gallate, The total of (−)-catechin gallate, (−)-epigallocatechin gallate, and (−)-gallocatechin gallate was defined as the catechin content.
Apparatus: Alliance HPLC / PDA system (Nippon Waters Corporation)
Column: Mightysil RP-18 GP, 4.6 mmφ × 150 mm (5 μm) (Kanto Chemical Co., Inc.)
Mobile phase: Liquid A Acetonitrile: 0.05% phosphoric acid water = 25: 1000
B liquid Acetonitrile: 0.05% phosphoric acid water: methanol = 10: 400: 200 (volume ratio)
Gradient: Linear gradient flow rate reaching from 100% A solution to 100% B solution after 3 minutes and 25 minutes after injection: 1 ml / min
Detection: UV230nm
Column temperature: 40 ° C

Example 1
<Prototype of catechin film>
A 2 wt% aqueous solution of polyphenone 70A (manufactured by Mitsui Norin Co., Ltd .; catechins 83 wt%, gallate catechin / non-gallate catechin = 12.35) was prepared as a catechin solution.

Further, methylcellulose (Metroses SM-4; manufactured by Shin-Etsu Chemical Co., Ltd.), hydroxypropyl methylcellulose (Metroses 60SH-06; manufactured by Shin-Etsu Chemical Co., Ltd.), polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), A 2% by weight aqueous solution of polyethylene glycol (Wako Pure Chemical Industries, Ltd.) was prepared.

A 10-ml catechin solution and 10 ml of a water-soluble polymer compound aqueous solution were mixed and subjected to centrifugal concentration to produce a thin film made of a catechin water-resistant product.

Add 100 ml of distilled water to this film, perform shaking extraction in a 40 ° C. hot water bath for 60 minutes, thoroughly stir and mix the extract, treat it with a 0.45 μm membrane filter, and determine the amount of catechins eluted by the above HPLC method. It was measured.

As a control, the amount of catechins eluted when the same treatment was performed using a solution obtained by mixing 10 ml of catechin solution with 10 ml of distilled water was measured, and the water resistance reaction rate of each catechin was determined using the following calculation formula. .

For each of the water-soluble polymer compounds, a film was manufactured and extracted and measured in the same manner for a mixture of a 2 wt% aqueous solution of polyphenone 70A containing 2 wt% ascorbic acid.

As a test comparison, a similar test was performed using a 2% by weight aqueous solution of carboxymethyl cellulose, which is a water-insoluble polymer compound, instead of the water-soluble polymer compound.

As shown in Table 1, a high water resistance reaction rate of catechins was observed in each water-soluble polymer compound. Moreover, the water-resistant reaction rate became higher by adding ascorbic acid. Looking at the water resistance reaction rate in each catechin, the gallate catechin showed a particularly high water resistance reaction rate.

Example 2
<Prototype of water resistant immobilization nonwoven fabric>
In addition to polyphenone 70A used in Example 1 as a catechin solution, tea extract polyphenone CH (Mitsui Norin Co., Ltd .; catechins 28 wt%, gallate catechin / non-gallate catechin = 1.88), tea extract Polyphenon G (Mitsui Norin Co., Ltd .; catechins 29 wt%, gallate catechin / non-gallate catechin = 1.28), tea extract Polyphenon KN (Mitsui Norin Co., Ltd .; catechins 32 wt%, gallate catechin / Non-gallate catechin = 1.08) and dissolved in a 2% by weight ascorbic acid aqueous solution so as to be 4% by weight as catechins.

Moreover, the methylcellulose used in Example 1 was dissolved in ethanol so that it might become 8 weight%, and each said catechin solution was mixed with equal amounts. 1 ml of this mixed solution was dropped onto a non-woven fabric cut into a 10 cm square, and dried to produce a catechin water-resistant fixed non-woven fabric.

Moreover, the nonwoven fabric which apply | coated only each catechin solution as a control, and the tea extract polyphenone NP (Mitsui Norin Co., Ltd .; containing 12 weight% of catechins, a gallate catechin / non-gallate catechin = 0.74) as a comparative example. The nonwoven fabric which performed the same process as the above using as a catechin solution and the nonwoven fabric which performed the same process as the above using the mixed liquid of the catechin solution and carboxymethylcellulose which used polyphenone 70A were also produced as an experiment.

<Measurement of water resistance reaction rate>
Each of the above catechins with water-resistant immobilization was placed in a sealed container, 50 ml of water was added, and the catechins were allowed to stand at 40 ° C. to conduct a catechin dissolution test. After 30 minutes, the solution from which the nonwoven fabric had been removed was treated with a 0.45 μm membrane filter, and the amount of catechins eluted was measured by HPLC. The removed non-woven fabric was dried with a dryer at 50 ° C. for 60 minutes, placed in a sealed container, and 50 ml of water was newly added to conduct a dissolution test in the same manner. This operation was repeated, a total of 5 dissolution tests were performed, and the water resistance reaction rate of each catechin with respect to the dissolution amount of the control was determined using the formula 1 shown above and judged (◎: Good, ○: Somewhat good, Δ: Somewhat bad, × bad).

When viewed from the ratio of gallate catechin / non-gallate catechin in the catechin solution, when the value is less than 0.8, the water resistance reaction rate is poor, whereas when it is 0.8 or more, the water resistance reaction is high. Showed the rate.

In addition, even when a catechin solution having a high ratio of gallate catechin / non-gallate catechin of 12.4 was used, as shown in Example 1, when treated with carboxymethylcellulose, the water resistance reaction rate of catechins was very high. It was very low.

Example 3
<Prototype of water-resistant catechins water-resistant immobilization filter>
As a catechin solution, 30 mg of polyphenone 70A (25 mg as catechins) is dissolved in 10 ml of a 60 vol% ethanol aqueous solution. To this, 5 mg, 12.5 mg, 25 mg, 50 mg, 125 mg, 250 mg, 1250 mg, 2500 mg of any of methylcellulose, hydroxypropylmethylcellulose, polyvinyl alcohol, and polyethylene glycol used in Example 1 was added, and stirred with catechins. A mixed solution of water-soluble polymer compound is prepared. These mixed solutions were dropped onto one piece of filter paper (Advantech, No. 5c, 110 mm) and dried to prepare a catechin water-resistant fixed filter.

<Measurement of deodorization rate>
The catechin water-resistant immobilization filter prototyped as described above is attached to the upper part of the 1 L wide-mouth bottle with tape, and 19 ml of water and a stirrer are placed in the lower part. Add 1 ml of 0.4% by weight aqueous ammonia solution, quickly cover with aluminum foil and seal. Stir at room temperature for 30 minutes, and then check the residual ammonia concentration in the headspace with a gas detector tube (Gastech, No. .3 La use).

Measurements were similarly made using a filter made as a control using only a catechin solution as a control, and a filter made using a solution prepared by dissolving 2500 mg of each water-soluble polymer compound in 10 ml of 60% by volume ethanol aqueous solution as a comparison. It was.
In the preliminary test, it was confirmed that the ammonia concentration in the liquid and the ammonia concentration in the air were in an equilibrium relationship.

Similarly, a prototype catechin water-resistant fixed filter is put in a sealed container, 50 ml of water is added, and the catechin is left at 40 ° C. to conduct an elution test. After 30 minutes, the solution from which the filter had been removed was treated with a 0.45 μm membrane filter, and the content of catechins eluted by the HPLC method was measured. The water resistance reaction rate of each catechin was determined. Moreover, after the taken-out filter was dried for 60 minutes with a 50 degreeC dryer, the deodorization rate was measured by the method similar to the above.

As shown in Table 3, the water-resistant reaction rate of catechins is 0.5 to 50 times higher in weight of the water-soluble polymer compound than catechins, and is further higher in 1 to 10 times weight. It was the highest at double weight. Moreover, before the elution test, it was found that all samples showed a high deodorization rate regardless of the water resistance reaction rate of the catechins, and that the water-soluble polymer compound did not reduce the deodorizing action of the catechins.

In the filter after the dissolution test, the higher the water resistance reaction rate of catechins, particularly gallate catechins, the higher the deodorization rate. From the above results, it was found that catechins can be fixed to a filter with water resistance by a water-soluble polymer compound, and furthermore, the deodorizing function of catechin can be sufficiently exhibited.

It was also found that a catechin water-resistant fixed filter can be provided in this example. In addition, the deodorizing function was hardly confirmed with the filter which apply | coated only the water-soluble polymer compound.

Example 4 <Prototype of catechin water-resistant fixed wood>
Polyphenone G aqueous solution was applied to the surface of a solid cedar wood having a thickness of 15 mm so as to be 10 g / m ² (2.9 g / m ² as catechins). After drying, methylcellulose was overcoated at 10 g / m ² and dried to produce a catechin water-resistant fixed wood. In addition, as a control, a sample coated only with a polyphenone G aqueous solution and a sample coated only with methylcellulose were also produced.

<Formaldehyde deodorization test>
The wood produced as a prototype by the above method is cut into 15 cm × 5 cm, and the mouth and back are covered with aluminum tape to obtain a test piece. A crystal dish containing 300 ml of purified water was placed at the bottom of a desiccator with an inner diameter of 24 cm, and a holder was placed on the crystal dish, in which 10 test pieces were stood radially. A filter paper (No. 5C, Advantech) having a diameter of 90 mm was attached to the inside of the lid of the desiccator, and 500 μl of about 4% formaldehyde aqueous solution was dropped therein, and the lid was quickly closed.

After these desiccators were allowed to stand at room temperature for 3 days, the formaldehyde concentration in the purified water was measured by the following method. The measured formaldehyde concentration was compared with the formaldehyde concentration of a blank test in which no test piece was put, and the difference between the two was taken as the formaldehyde concentration (adsorption amount) adsorbed by the test piece.

Moreover, after the said test, the filter paper affixed inside the desiccator lid was removed with the test piece remaining, and the lid was again capped with the purified water in the crystallization dish. After standing for 4 days, the formaldehyde concentration (re-release amount) re-released from the test piece into the purified water was measured. The absorption amount was determined from the difference between the adsorption amount and the re-release amount.

Also, when the catechin water-resistant fixed wood and the control were placed in a test environment container with a humidity of 75% RH and a temperature of 40 ° C. for 24 hours, and removed and rubbed with a white cloth, the degree of color transfer was evaluated on a three-point scale (3 Point: No color transfer, 2 points: Light color transfer, 1 point: Color transfer, 0 point: Strong color transfer) Visually observed, and combined with formaldehyde absorption, comprehensively judged as functional wood ( A: Good, ○: Somewhat good, Δ: Somewhat bad, ×: Bad).

≪Formaldehyde measurement conditions≫
The amount of formaldehyde transferred into the purified water was determined by adding 1 ml of DNPH reagent (0.24% DNPH / 2N-HCl) to 1 ml of the solution and reacting at room temperature for about 30 minutes to derivatize formaldehyde into DNPH. Measured by HPLC.
Apparatus: Alliance HPLC / PDA system (Nippon Waters Corporation)
Column: Mightysil RP-18 GP, 4.6 mmφ × 150 mm (5 μm) (Kanto Chemical Co., Inc.)
Mobile phase: 50% aqueous acetonitrile flow rate: 1 ml / min
Detection: UV355nm
Column temperature: 40 ° C

As shown in Table 4, it was confirmed that the wood in which catechins were water-resistant fixed with methylcellulose had a remarkable color transfer preventing effect, although the amount of formaldehyde absorbed was almost the same as that of the control.

From the above results, it was found that catechins can be made water resistant while maintaining the formaldehyde removal function of catechins, and it is possible to provide a woody material in which catechins are water-resistant fixed.

Example 5
<Masking agent>
A tablet was made according to the formulation shown in Table 5. A coating solution comprising 2 parts by weight of ascorbic acid, 4 parts by weight of polyphenone 70A, 8 parts by weight of methylcellulose, 40 parts by weight of ethanol, and 46 parts by weight of water with respect to 1 kg of the tableted tablet 30 at a rate of 6 g / min. Sprayed and coated for minutes. About the obtained tablet, compared with the thing which did not coat | cover, the 4-degree evaluation of the degree of unpleasant taste felt when it was included in the mouth by a sensory test (4: not felt, 3: almost not felt, 2 : Feel a little, 1: Feel) and calculate the average. The results are shown in Table 5. This test was conducted by 10 panelists.

As shown in Table 5, it was revealed that the tablets coated with the catechin water-resistant product of the present invention are excellent in the masking action of unpleasant taste.

Example 6
<Catechin powder>
The same amount of 10% by weight methylcellulose aqueous solution was added to 5% by weight polyphenone 70A aqueous solution and mixed by stirring to produce a catechin water-resistant product. This was centrifuged (16,000 rpm × 10 min), and the supernatant was removed. Distilled water was added to the remaining water-resistant product and centrifuged again under the same conditions to wash the water-resistant product. This washing process was repeated a total of 3 times, and the obtained water-resistant product was dried and then finely pulverized with a pulverizer to obtain a catechin water-resistant product powder.

Cookies, candy, chocolate, udon, spaghetti, bread, cereal, ice cream, yogurt, jelly, tea drinks, soft drinks, grilled meat sauce, dressing As a result of trial manufacture of retort curry, soup, kamaboko, and sausage, the bitter and astringent taste derived from catechins was effectively suppressed in all foods, and it was suitable for intake of a large amount of catechins.

Example 7
<Catechin underwear>
As a catechin solution, polyphenone 70A was dissolved in an aqueous solution of 2% by weight ascorbic acid so as to be 5% by weight. Moreover, hydroxypropyl methylcellulose was dissolved in ethanol so that it might become 10 weight%, and each said catechin solution was mixed with equal amounts. A 100% cotton underwear knitted fabric was impregnated in a mixed solution of 200% of the weight of the fabric and dried at 100 ° C. to prepare a catechin water-resistant fixed underwear.

Example 8
<Catechin mask>
A 1 wt% aqueous solution of polyphenone 70A was prepared as a catechin solution. Moreover, methylcellulose was dissolved in ethanol so that it might become 2 weight%, and each said catechin solution was mixed with equal amounts. This solution was dropped onto the nonwoven fabric so as to be 50 ml / m ² to obtain a catechin water-resistant fixed nonwoven fabric. The catechin water-resistant immobilization nonwoven fabric was sandwiched between two other nonwoven fabrics, cut into a size of 20 cm × 15 cm, and the ends were adhered while sandwiching a rubber cord to prepare a catechin mask.

Example 9
<Catechin rubber gloves>
A 2% by weight aqueous solution of polyphenone 70A was prepared as a catechin solution and mixed in an equal amount with a 2% by weight aqueous solution of methylcellulose. This solution was dispersed in a synthetic rubber latex in a colloidal aqueous dispersion, and after aging, hand-type dipping was performed. After forming by dipping twice, a vulcanizing agent (sulfur) was added, heated and dried, and removed from the mold to produce a catechin rubber glove.

As described above, the water resistance method for catechins of the present invention can efficiently produce a catechin water-resistant product and a catechin water-resistant fixed product that retains the function of catechins, and has complicated processes and new equipment. It is a simple method that is not necessary.

Claims (16)

One selected from catechins having a weight ratio A / B of 0.8 or more of gallate catechin (A) and non-gallate catechin (B), water-soluble cellulose ethers, polyalkyl ethers and polyvinyl alcohols Alternatively, a water resistance method for catechins, comprising mixing and reacting two or more water-soluble polymer compounds. One selected from catechins having a weight ratio A / B of 0.8 or more of gallate catechin (A) and non-gallate catechin (B), water-soluble cellulose ethers, polyalkyl ethers and polyvinyl alcohols Alternatively, a water resistance method for catechins comprising mixing two or more water-soluble polymer compounds and reacting them under acidic conditions. One or two or more water-soluble polymer compounds selected from water-soluble cellulose ethers, polyalkyl ethers and polyvinyl alcohols are 0.5 to 50 times the weight of catechins. The water resistance method according to claim 1 or 2. The water-soluble cellulose ether is one or more water-soluble polymer compounds selected from methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl methyl cellulose, and the polyalkyl ethers are polyethylene glycol, polypropylene glycol and trimethylolpropane polypropylene glycol ether. The water resistance method according to any one of claims 1 to 3, wherein the water-soluble polymer compound is one or more water-soluble polymer compounds selected from the group consisting of polyvinyl alcohols. A catechin water-resistant product obtained by the water resistance method according to claim 1. A deodorant comprising the catechin water-resistant product according to claim 5. A food or a raw material thereof containing the water-resistant catechin according to claim 5. 6. A formed article on which the catechin water-resistant product according to claim 5 is supported. 5. A catechin water-resistant immobilization formed product, wherein the catechin is water-immobilized to the formed product using the water resistance method according to claim 1. 10. The catechin water-resistant immobilization formed product according to claim 9, wherein the formed product is a fiber. The catechin water-resistant immobilization formed product according to claim 9, wherein the formed product is a woody material. 10. The catechin water-resistant immobilization formed product according to claim 9, wherein the formed product is rubber. 10. The catechin water-resistant immobilization formed product according to claim 9, wherein the formed product is a plastic. The catechin water-resistant immobilization formed article according to claim 9, wherein the formed article is a material for construction and furniture. 10. The catechin water-resistant immobilization formed product according to claim 9, wherein the formed product is a sheet. 10. The catechin water-resistant immobilization formed product according to claim 9, wherein the formed product is a filter.