JP5032034B2 - Method for water-resistant immobilization of catechins to formations - Google Patents

Description

A catechin is formed by mixing a water-soluble polymer compound and catechin in a water-containing organic solvent, and then applying the mixed solution to the formed product and further drying to remove the solvent. The present invention relates to a method for fixing water-resistant to objects.

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, when a filter or the like is washed with water, the applied catechins are eluted, and the antibacterial and deodorizing properties are greatly reduced. In addition, when catechins are carried on a sheet or the like, 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).

In addition, when commercializing a product in which water-resistant catechins are immobilized, the water-resistant catechins are uniformly and easily immobilized on the product in order to homogenize the quality and performance of the product. Technology was sought.

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

The object of the present invention is to overcome the above-mentioned problems and to fix catechins to a formed product with water resistance.

As a result of intensive investigations to achieve the above object, the present inventors have made water resistance with a water-soluble polymer compound when the ratio of gallate catechins to non-gallate catechins in catechins, which are low molecular polyphenols, is specific. And the water-resistant reaction of catechins by the water-soluble polymer compound does not occur in the water-containing organic solvent, and the present invention has been completed.

The present invention according to claim 1 is the one or more water-soluble polymer compounds selected from water-soluble cellulose ethers, polyalkyl ethers and polyvinyl alcohols, gallate catechins (A) and non-gallate catechins. It is a mixed solution in which a catechin having a weight ratio A / B of (B) of 0.8 or more is mixed with a water-containing organic solvent.

Moreover, this invention of Claim 2 is a mixed solution of Claim 1 whose water-containing organic solvent is acidic .

In the invention according to claim 3 , the amount of one or more water-soluble polymer compounds selected from water-soluble cellulose ethers, polyalkyl ethers and polyvinyl alcohols relative to catechins is 0. a mixed solution according to claim 1 or 2, characterized in that 5 to 50 times by 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. The mixed solution 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 there.

The present invention according to claim 5 is the mixed solution according to any one of claims 1 to 4, wherein the concentration of the organic solvent in the mixed solution is 30% by volume to 95% by volume.

Further, the invention described in claim 6, water-containing organic solvent is methanol, ethanol, propanol, isopropanol, acetone, methyl isobutyl ketone, is selected from acetonitrile or mixtures thereof, according to any of claims 1 to 5 It is a mixed solution.

Further, the invention of claim 7, applied to formation of the mixed solution according to any one of claims 1 to 6, characterized by comprising the further dried by removing the solvent, catechins This is a method for fixing water to a formed product.

The present invention according to claim 8 is the method according to claim 7 , wherein the material of the formed material is any one of fibers, woody materials, rubbers, and plastics.

The present invention according to claim 9 is the method according to claim 7 , characterized in that the use of the formed material is any one of a building / furniture material, sheets, and a filter.

The water-resistant immobilization method of the present invention enables catechins to be uniformly water-resistant immobilized on various materials without going through complicated steps. Thereby, elution of catechins from the formed product by washing or the like can be suppressed. Furthermore, catechins retain various functions even when they are water-resistant fixed to the formed product. Further, 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 even in a mixed solution state.

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. and Matsumoto Yushi Seiyaku Co., Ltd.

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. It is sold by Asahi Denka Kogyo Co., Ltd. and Nippon Oil & Fat Co., Ltd.

Since the water resistance reaction between catechins and water-soluble polymer compounds is promoted under acidic conditions, the water resistance of catechins can be further improved by acidifying the solution in which catechins and / or water-soluble polymer compounds are dissolved. 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 water resistance reaction rate of catechins is high in gallate catechins among catechins, and the weight ratio A / B of gallate catechins (A) and non-gallate catechins (B) in the catechins used is 0.8 or more. It is preferably 1.0 or more, more preferably 1.2 or more, still more 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.

In the present invention, catechins are water-resistant by mixing a catechin solution and a water-soluble polymer compound solution. 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-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, the water-resistant polymer compound is not water-resistant and maintains a dispersion solution. In the case of a solvent, it is made water resistant by the contained water as the organic solvent concentration is lowered 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 fix the catechins to the formed product in a water-resistant manner through a process of making the water resistant while removing the solvent.

When this method is used, it becomes possible to uniformly support the catechins and the water-soluble polymer compound in one step in producing a formed product in which the catechins are water-resistant fixed by the water-soluble polymer compound. It is possible to fix catechins having water resistance without greatly changing existing facilities and processes.

The organic solvent used in the present invention is preferably one that exhibits hydrophilicity and volatility such as methanol, ethanol, propanol, isopropanol, acetone, methyl isobutyl ketone, and acetonitrile, but is not limited thereto, and the solvents shown above And mixed solvents containing other solvents may be used. From the viewpoint of ease of handling, safety, and versatility, it is most preferable to use alcohols, particularly ethanol.

The concentration of the organic solvent in the mixed solution of the water-soluble polymer compound and catechins is preferably 30% by volume to 95% by volume, more preferably 35% by volume to 90% by volume, and more preferably 40% by volume to 40% by volume from the viewpoint of stability and workability. 80% by volume is particularly preferred, most preferably between 50% and 60% by volume. When the organic solvent concentration is low, a water-resistant product is formed by the water-soluble polymer compound and catechins. When the organic solvent concentration is high, the water-soluble polymer compound is precipitated, resulting in a non-uniform solution. In general, 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. When the concentration of the water-soluble polymer compound in the mixed solution increases, Keeps the dispersion stable even when the temperature is low.

The concentration of the water-soluble polymer compound and the catechins in the mixed solution is preferably from 0.01% to 20% from the viewpoint of ease of handling 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 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.

Catechins that are water-resistant with methylcellulose and / or hydroxypropylmethylcellulose, which are food additives, can also be used in foods. 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. Catechins that have been water-resistant with methylcellulose and / or hydroxypropylmethylcellulose also have the effect of suppressing the diffusion of bitter and astringent ingredients derived from catechins in the oral cavity, and are used as foods and their raw materials as various edible compositions. 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. By the water-resistant immobilization method of the present invention, catechins can be water-immobilized to various formed products.

Formed products are classified according to their use, in addition to the foods or their raw materials, there are building / furniture materials, sheets, filters, etc. There are woody materials, rubbers and plastics.

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 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

Test example 1
<Prototype of water-resistant catechin>
A 2 wt% aqueous solution of polyphenone 70A (manufactured by Mitsui Norin Co., Ltd .; catechins 83 wt%, gallate catechin / non-gallate catechin = 12.35) as a catechin solution was prepared. 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 catechin water-resistant product was produced by mixing 10 ml of the catechin solution and 10 ml of the water-soluble polymer compound aqueous solution.

This solution is centrifuged to dry the water-resistant product, 100 ml of distilled water is added, the mixture is shaken and extracted in a 40 ° C. hot water bath for 60 minutes, and the extract is stirred and mixed well, and then treated with a 0.45 μm membrane filter. The amount of catechins eluted by the HPLC method 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. .

In each water-soluble polymer compound, a catechin water-resistant product was similarly produced for a mixture of a 2 wt% polyphenone 70A aqueous solution containing 2 wt% ascorbic acid, and the amount of catechins eluted was measured.

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. However, the catechin water-resistant product produced by mixing the catechin aqueous solution and the water-soluble polymer compound aqueous solution is insoluble and thus has poor uniformity, and it seems difficult to produce a formed product on which it is immobilized.

Example 1
<Prototype of a mixed solution of water-soluble polymer compound and catechin>
The catechin solution was dissolved in a special grade ethanol solution (manufactured by Kishida Chemical Co., Ltd .; purity 99.5%) using Polyphenon 70A in the same manner as in Test Example 1 so as to be 2% by weight.

Further, methylcellulose, hydroxypropylmethylcellulose, polyvinyl alcohol, and polyethylene glycol used in Test Example 1 as water-soluble polymer compounds are dispersed and dissolved in a special grade ethanol solution so as to be 2% by weight, and mixed with each of the above catechin solutions in equal amounts. Then, a mixed ethanol solution of a water-soluble polymer compound and catechin was prototyped. Change the ethanol concentration of the catechin solution and the water-soluble polymer compound solution to 95, 90, 80, 60, 50, 40, 35, 30, 20% by volume, and similarly mix the water-soluble polymer compound and the catechin mixed solution. We made a prototype and observed the ethanol concentration in the mixed solution and the stability of the solution. Moreover, the mixed solution was dried to prepare a catechin water-resistant product, and the workability was evaluated.
Further, the same test was conducted with respect to hydroxypropylmethylcellulose while changing its final concentration to 0.5% by weight and 0.1% by weight.

As shown in Table 2, when the ethanol concentration of the mixed solution was lower than 30% by volume, water-resistant products were formed between many water-soluble polymer compounds and the catechin solution, which was in a non-uniform state. As the concentration increased, the state of the mixed solution decreased from white turbidity, and the stability of the solution increased to clear. Moreover, as the ethanol concentration increased, the time required for drying was shortened, and the workability for producing catechin water-resistant products was excellent.

However, when it exceeded 90% by volume, the solution started to become thin again due to the precipitated water-soluble polymer compound, and the stability was somewhat inferior. When this mixed solution was dried to increase the water concentration in the solution, a catechin water-resistant product was produced even with a clear solution, but a 100% by volume concentration containing almost no water was found to produce a water-resistant product. I couldn't. In addition, hydroxypropylmethylcellulose, which is originally highly soluble in organic solvents, has a higher ethanol concentration than other water-soluble polymer compounds, and its final concentration is 1.0% by weight, 0%. It was observed that the composition was stabilized at a higher ethanol concentration as it was changed to 0.5 wt% and 0.1 wt%.

Example 2
<Prototype of a mixed solution of water-soluble polymer compound and catechin>
In the same manner as in Example 1, polyphenone 70A was used as a catechin solution and was prepared to be 2% by weight in a 95% by volume ethanol aqueous solution. Similarly, methylcellulose as a water-soluble polymer compound is dissolved in a 95% by volume aqueous ethanol solution to 2% by weight and mixed with the above catechin solution in an equal amount to obtain a mixed solution of water-soluble polymer compound and catechin (ethanol concentration 95 volume). %). When the ethanol concentration of the catechin solution and the 2% by weight methylcellulose solution was changed to 80, 60, 50, 40, 30, 25% by volume, a mixed solution was also made in the same way, and the ethanol concentration in the mixed solution and the stability of the solution were obtained. Was observed.

Alcohols such as special grade methanol (made by Kishida Chemical Co., Ltd.), special grade 2-propanol (made by Kanto Chemical Co., Ltd.), special grade acetone (made by Kishida Chemical Co., Ltd.) and special grade acetonitrile (made by Kishida Chemical Co., Ltd.) instead of ethanol The same test was performed, and each organic solvent concentration and the stability of the solution were observed.

As a comparative example, the same test was performed using glycols such as special grade ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) and special grade propylene glycol (made by Wako Pure Chemical Industries, Ltd.).

As shown in Table 3, the same results were obtained when various organic solvents were used as examples instead of ethanol. In the case of alcohols, 50 to 95% of methanol, 40 to 95% of ethanol, and 30 to 95% of propanol, and the mixed solution was clarified at a lower organic solvent concentration as the alkyl chain lengthened. These alcohols were preferred because they had no odor and were easy to handle.

Acetone and acetonitrile remained stable even at low organic solvent concentrations, but the characteristic odor was conspicuous. As for the glycols used as comparative examples, it was not confirmed that the solution was stably stabilized even at a high organic solvent concentration. Moreover, since glycols also have a melting point near 200 ° C., catechin was not solidified even when this mixed solution was dried.

Example 3
<Prototype of water resistant fixed nonwoven fabric for catechin>
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 catechins / 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 a special grade ethanol solution so as to be 8% by weight, and each was mixed with the above catechin solution in an equal amount (final concentration of ethanol 50% by volume). A 1-ml drop of this mixed solution was applied to a non-woven fabric cut into a 10 cm square, dried, and a non-woven fabric in which catechin was fixed with water resistance was prepared.

Moreover, using only each catechin solution as a control, tea extract polyphenone NP (manufactured by Mitsui Norin Co., Ltd .; containing 12% by weight of catechins, gallate catechin / non-gallate catechin = 0.74) was used as a comparative example. Using the solution, a non-woven fabric subjected to the same treatment as described above was also produced.

<Measurement of water resistance reaction rate>
Each of the above catechin water-resistant immobilization nonwoven fabrics was put in a sealed container, 50 ml of water was added, and the mixture was left 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).

According to the ratio of gallate catechin / non-gallate catechin in the catechin solution, when the value is less than 0.8, the water-resistant reaction rate is poor, whereas when it is 0.8 or more, the ratio depends on the ratio. In particular, gallate catechins remained in a large amount even after repeated extraction five times.

Example 4
<Prototype of catechin waterproof 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 filter paper (Advantech, No. 5c, 110 mm) and dried to produce a catechin water-resistant fixed filter.

<Measurement of deodorization rate>
The catechin water-resistant immobilization filter produced as described above is affixed to the upper part of the 1 L wide-mouth bottle with tape, and 19 ml of water and a stirring bar 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). As a control, a filter made using only 1 ml of a 3.0% by weight aqueous solution of polyphenone 70A, and as a comparison, a filter made using a solution obtained by dissolving only 2500 mg of each water-soluble polymer compound in 10 ml of a 60 vol% ethanol aqueous solution. Measurements were made in the same manner. 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 filter is put in a sealed container, and 50 ml of water is added and left at 40 ° C. to conduct the dissolution 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 5, the water resistance 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, regardless of the water resistance reaction rate of the catechins, all samples showed a high deodorization rate, and it was found 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. The filter using only the water-soluble polymer compound hardly confirmed the deodorizing function.

Example 5
<Prototype of catechin water-resistant fixed wood>
Methyl cellulose is dissolved in a special grade ethanol solution so as to be 0.1% by weight. An equal amount of 0.1% by weight polyphenone G aqueous solution is mixed with this and stirred to prepare a mixed solution. This mixed solution was applied to the surface of a solid cedar having a thickness of 15 mm so as to have a density of 20 l / m ² (2.9 g / m ² as catechins) and dried to produce a catechin water-resistant fixed wood. In addition, as a control, a solution in which an equal amount of ethanol was mixed with an aqueous polyphenone G solution and a solution in which an equal amount of pure water was mixed with a methylcellulose ethanol solution were applied as prototypes.

<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-coated 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 taken out and rubbed with a white cloth, the degree of color transfer was evaluated on a 3-point scale (3 points: color No transfer, 2 points: light color transfer, 1 point: color transfer, 0 point: strong color transfer) Visual observation, and combined with formaldehyde absorption, comprehensively judged as functional wood (◎: good , ○: Somewhat good, Δ: Somewhat bad, ×: Bad).

≪Formaldehyde measurement conditions≫
The amount of formaldehyde transferred to 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% acetonitrile aqueous solution
Flow rate: 1 ml / min
Detection: UV355nm
Column temperature: 40 ° C

As shown in Table 6, it was confirmed that the wood in which catechins were water-fixed with methylcellulose had almost the same amount of formaldehyde absorption as compared with the control, but greatly suppressed color transfer. From the above results, it was found that catechins can be fixed with water resistance while retaining the formaldehyde removal function of catechins, and it is possible to provide a woody material with catechins fixed with water resistance.

Example 6
<Masking agent>
A tablet was made according to the formulation shown in Table 7. 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 a special grade ethanol solution, and 46 parts by weight of water with respect to 1 kg of this tableting tablet is 6 g / min. Spray coated for 30 minutes and coated. 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 7. This test was conducted by 10 panelists.

As shown in Table 7, it was revealed that the tablets coated with the catechin water-resistant product of the present invention were excellent in the masking action of unpleasant taste.

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. Further, hydroxypropylmethylcellulose was dissolved in a special grade ethanol solution so as to be 10% by weight and mixed with the above catechin solution in an equal amount. 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 an underwear containing catechin.

Example 8
<Catechin mask>
A 1 wt% aqueous solution of polyphenone 70A was prepared as a catechin solution. Further, methylcellulose was dissolved in a special grade ethanol solution so as to be 2% by weight, and each was mixed with the above catechin solution in an equal amount. 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. A 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 water absorption sheet>
A 1 wt% aqueous solution of polyphenone 70A was prepared as a catechin solution. Further, methylcellulose was dissolved in a special grade ethanol solution so as to be 2% by weight, and each was mixed with the above catechin solution in an equal amount. This mixed solution was dropped onto a polyethylene film so as to be 100 ml / m ^2, and then placed in a dryer at 50 ° C. and dried for about 1 hour. This catechin water-resistant fixed film was used as a water-impermeable sheet, and a water-absorbing polymer fine powder composed of polyacrylic acid was fixed thereon in a layered manner using a binder resin. A water-permeable sheet made of non-woven fabric was coated with an adhesive in a dot pattern, and a non-water-permeable sheet and a water-permeable sheet were adhered to cover the surface to prepare a catechin water-absorbing sheet.

  As described above, the method for water-resistant fixing of catechins of the present invention to the formed product can uniformly fix the catechins to the formed product while maintaining the function of the catechins, This is a simple method that does not require new equipment.

Claims (9)

Weight ratio A / B of one or more water-soluble polymer compounds selected from water-soluble cellulose ethers, polyalkyl ethers and polyvinyl alcohols, and gallate catechin (A) and non-gallate catechin (B) A mixed solution in which a catechin having a ≧ 0.8 is mixed with a water-containing organic solvent. The mixed solution according to claim 1, wherein the hydrous organic solvent is acidic. The amount of one or more water-soluble polymer compounds selected from water-soluble cellulose ethers, polyalkyl ethers and polyvinyl alcohols relative to catechins is 0.5 to 50 times weight. The mixed solution according to claim 1. 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 mixed solution according to any one of claims 1 to 3, wherein one or two or more water-soluble polymer compounds selected from the group consisting of polyvinyl alcohols are polyvinyl alcohols. 5. The mixed solution according to claim 1, wherein the concentration of the organic solvent in the mixed solution is 30% to 95% by volume. The mixed solution according to any one of claims 1 to 5, wherein the hydrous organic solvent is selected from methanol, ethanol, propanol, isopropanol, acetone, methyl isobutyl ketone, acetonitrile, or a mixture thereof. A method for water-fixing catechins to a formed product, comprising the steps of applying the mixed solution according to any one of claims 1 to 6 to the formed product and further drying to remove the solvent. 8. The method according to claim 7, wherein the material of the formed material is any one of fibers, wood materials, rubbers and plastics. 8. The method according to claim 7, wherein the use of the formed material is any one of an architectural / furniture material, sheets, and a filter.