Granulated product, composition, and method for deodorizing malodorous component

Abstract

To provide a granule excellent in storage stability and fluidity while having a high deodorizing effect, a composition using the granule, and a method for deodorizing a malodorous component using the composition.SOLUTION: A granule comprising a core portion comprising a porous support and a laccase supported on the porous support. The granulated product and a compound having a phenolic hydroxyl group. A method for deodorizing a malodorous component, comprising bringing the granulated product or the composition into contact with the malodorous component to deodorize the malodorous component.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a granulated material suitable for a deodorant composition, a composition using the granulated material, and a method for deodorizing malodorous components using the composition. [Background technology]

[0002] Examples of malodorous components present in our daily lives include nitrogen-containing compounds such as trimethylamine and sulfur-containing compounds such as methyl mercaptan. Deodorant compositions and methods have been reported that have a high deodorizing effect against these malodorous components and high storage stability.

[0003] Patent document 1 discloses that the storage stability of enzyme-containing granules can be improved by adjusting the pH of the enzyme mixture supplied to the laccase granule formation process to a value higher than 7 in order to prevent a decrease in the enzymatic activity of the laccase-containing granules.

[0004] Patent Documents 2 to 4 disclose that, in order to avoid limitations when used as a deodorizer, adding a metal salt to a mixture of a polyphenol compound and an alkaline substance allows the deodorizing effect to be exerted quickly and within a short period of time. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 4944036 [Patent Document 2] Patent No. 5704813 [Patent Document 3] Patent No. 5850999 [Patent Document 4] Patent No. 6023946 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the above deodorant composition and method still have room for improvement in terms of achieving both a high deodorizing effect and high storage stability.

[0007] The present invention has been made in consideration of the above circumstances, and an object of the present invention is to provide a granulated product that has a high deodorizing effect while also being excellent in storage stability and fluidity, a composition using the granulated product, and a method for deodorizing malodorous components using the granulated product or the composition. [Means for solving the problem]

[0008] The present invention includes the following aspects. [1] A granulated product comprising a porous support and laccase supported on the porous support. [2] The granulated product according to [1], which is a granulated product obtained by stirring and granulating the porous support and the laccase. [3] The granulated product according to [1] or [2], further comprising a compound having a phenolic hydroxyl group. [4] The granulated material according to [3], which contains a compound having a phenolic hydroxyl group supported on the porous support. [5] A granulated material according to [3], in which a compound having a phenolic hydroxyl group is attached to at least a portion of the surface of the granules obtained by stirring and granulating the porous support and the laccase. [6] A granulated material according to [3], in which a compound having a phenolic hydroxyl group and hydrophilic inorganic microparticles are attached to at least a portion of the surface of the granules obtained by stirring and granulating the porous support and the laccase. [7] The granule according to any one of [3] to [6], wherein the compound having a phenolic hydroxyl group is at least one selected from the group consisting of tannic acid, ferulic acid, catechins, lignin sulfonates, gallic acid, propyl gallate, coffee bean extract components, grape seed extract components, and green tea extract-containing components. [8] The granulated product according to any one of [1] to [7], further comprising a polyhydric alcohol. [9] The granule according to [8], wherein the polyhydric alcohol is glycerin.

[10] A composition comprising the granulated product according to any one of [1] to [9] and a compound having a phenolic hydroxyl group.

[11] A method for deodorizing a malodorous component, comprising contacting the granule according to any one of [1] to [9] or the composition according to

[10] with the malodorous component to deodorize the malodorous component.

[12] The method for deodorizing a malodorous component according to

[11] , wherein the granulated material is brought into contact with the malodorous component in the presence of water. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a granulated product that has a high deodorizing effect while also having excellent storage stability and flowability, a composition using said granulated product, and a method for deodorizing malodorous components using said granulated product or said composition. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic cross-sectional view of a granulated product according to a first embodiment of the present invention. [Figure 2] 1A is a schematic cross-sectional view of a granulated product according to a second embodiment of the present invention, and FIG. 1B is a schematic cross-sectional view of a granulated product according to a third embodiment of the present invention. [Figure 3] 1A is a schematic cross-sectional view of a granulated product according to a fourth embodiment of the present invention, and FIG. 1B is a schematic cross-sectional view of a granulated product according to a fifth embodiment of the present invention. [Figure 4] FIG. 10 is a schematic cross-sectional view of a granulated material contained in a composition according to a sixth embodiment of the present invention. [Figure 5] 1 is a microscope image of the surface of a granulated product (granulated product 2) according to the first embodiment of the present invention, which is produced by stirring and mixing. [Figure 6] 1 is an image of the surface of a granulated product (granulated product 2) according to a first embodiment of the present invention, which is produced by stirring and mixing, observed under a microscope, in which the unevenness of the surface is displayed using shades of color. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The following present embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following content. The present invention can be modified in various ways without departing from the gist of the present invention.

[0012] In this specification, the term "granules" refers to an aggregate (average particle size: 1 mm or more) that is composed of a large number of fine particles and maintains fluidity as a whole. In this specification, the term "powder" refers to an aggregate (average particle size: less than 1 mm) that is composed of a large number of fine particles and maintains fluidity as a whole. In the present specification, the average particle size of the granulated material, the powder and particles contained in the composition, and the hydrophilic inorganic fine particles can be measured, for example, by laser diffraction, and the 50% integrated value of the obtained particle size distribution (integral distribution curve) is determined as the average particle size.

[0013] <Granulation> The granulated material of this embodiment includes a porous support and laccase supported on the porous support.

[0014] In the granulated material of this embodiment, the laccase is protected by being supported within the porous structure of the support, and contact with moisture and other substances in the environment is reduced, making it less susceptible to the influence of the surrounding environment and increasing the storage stability of the laccase.

[0015] The granules of this embodiment are preferably those obtained by stirring and granulating a porous support and laccase. The granules obtained by stirring and granulation have fine irregularities on the surface. If the granules of this embodiment are those obtained by stirring and granulation, the surface area of ​​the granules increases significantly, making it easier for water, which is the trigger component for the deodorizing effect, to penetrate into the recesses on the surface of the granules, and therefore easier for the laccase held inside the porous material to come into contact with water. Furthermore, unlike powder, the granulated material of this embodiment is less likely to scatter, has excellent fluidity, and is easy to handle. A specific method for stirring and granulating will be explained in the method for producing granulated products described below.

[0016] <Porous support> The porous support used in this embodiment may be any porous particle capable of supporting laccase. Typically, the laccase is supported on the porous support by impregnating the porous support with laccase. The porous support may be, for example, one or more selected from activated carbon, zeolite particles, bentonite particles, activated alumina particles, activated clay, calcium silicate particles, and diatomaceous earth.

[0017] The porous support preferably has a pore volume of 0.2 mL / g to 2.0 mL / g as measured by nitrogen gas adsorption. The porous support preferably has a specific surface area of ​​5 m2 or less as measured by nitrogen gas adsorption. 2 / g~2000m 2 / g, and 50m 2 / g~1500m 2 / g is more preferred.

[0018] <Laccase> The laccase used in this embodiment is not particularly limited as long as it has laccase enzymatic activity, and may be produced by a conventional method or may be appropriately selected from commercially available products. The laccase used in this embodiment may be in a purified state or in a crude enzyme state. The laccase used in this embodiment may be in a dissolved state in a liquid or in a suspended state.

[0019] The enzymatic activity of laccase can be measured by a known method using a liquid containing laccase as an enzyme (sometimes referred to herein as an "enzyme liquid"). In the present specification, the enzyme activity of laccase means laccase activity unless otherwise specified. Known methods include, for example, the use of ABTS, i.e., 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt, C 18 H 16 N4S4(NH4)2) can be used as the substrate. More specifically, an ABTS aqueous solution, a buffer solution, and an enzyme solution are prepared, and the reaction solution obtained by mixing these is used as the sample. In this sample, ABTS is oxidized by the enzymatic action of laccase. Since the ABTS oxide has a high absorbance at a wavelength of 420 nm, the ABTS aqueous solution is originally transparent, but when oxidized by laccase, its color changes to blue. After mixing (in other words, after the start of the reaction), the absorbance A at a wavelength of 420 nm for this sample is measured for a certain period of time (for example, several minutes). 420 is continuously measured, and A 420 The increase in absorbance at a wavelength of 420 nm, ΔA 420 The corresponding reaction time (min) is then calculated. The enzyme activity of laccase can be calculated by substituting each value into the following formula (i). In formula (i), "36" refers to the molar extinction coefficient of ABTS at a wavelength of 420 nm (36000 M -1 ·cm -1 ) comes from [Laccase enzyme activity (U / mL)] = {ΔA 420 × [reaction solution volume (mL)]} / {[reaction time (min)] × 36 × [enzyme solution volume (mL)]} (i) Here, the total enzyme activity of laccase, 1 U, is defined as the amount of enzyme that oxidizes 1 μmol of ABTS in 1 minute through the above reaction, and satisfies the relationship of the following formula (ii). [Total enzyme activity of laccase (U)] = [Enzyme activity of laccase (U / mL)] × [Volume of enzyme solution (mL)] (ii)

[0020] The enzymatic activity of the laccase is preferably 10 U / g or more, more preferably 30 U / g or more, and may be, for example, 50 U / g or more, relative to the mass of the granulated product of this embodiment. When the enzymatic activity of the laccase is equal to or greater than the above-mentioned lower limit, a high deodorizing effect can be obtained even when the amount of enzyme used is reduced. In addition, odors that are easily detected by humans can be more easily eliminated. On the other hand, there is no particular upper limit to the enzymatic activity of laccase. For example, laccase with an enzymatic activity of 500 U / g or less can be more easily obtained.

[0021] The amount of the enzyme solution contained in the granules of this embodiment is usually 1 to 40 parts by mass, and may be 10 to 30 parts by mass, per 100 parts by mass of the support. When the amount of the enzyme solution is within the above range, a granules having appropriate storage stability tends to be obtained.

[0022] The average particle size of the granulated product in this embodiment is usually 1 mm to 20 mm, but may be 1 mm to 10 mm, or 1.5 mm to 6.0 mm. When the average particle size of the granulated product is within the above range, granulated product with excellent flowability tends to be easily obtained.

[0023] Other ingredients The granules of this embodiment may contain other components (sometimes referred to herein as "other components (1)") in addition to the porous support and laccase, as long as the effects of the present invention are not impaired. The other components (1) can be selected arbitrarily depending on the purpose and are not particularly limited.

[0024] To further enhance storage stability, the granulated product of this embodiment may contain components such as polyhydric alcohols such as polyethylene glycol, ethylene glycol, propylene glycol, and glycerin; disaccharides, sorbitol, dextran, polyvinylpyrrolidone, and dimethyl sulfoxide. Among these, polyhydric alcohols are preferred, and glycerin is more preferred. The inclusion of these components in the granulated product improves the water retention of the granulated product and makes it less likely that the enzymatic activity of the laccase will decrease, thereby further enhancing storage stability. The amount of polyhydric alcohol such as glycerin contained in the granules of this embodiment is preferably 4.0 to 7.0 parts by mass, and more preferably 5.0 to 6.0 parts by mass, per 100 parts by mass of the total mass of the granules. When the amount of polyhydric alcohol such as glycerin is at or above the lower limit of the above range, the effect of improving the water retention of the granules is more easily exhibited. On the other hand, when the amount of polyhydric alcohol such as glycerin is at or below the upper limit of the above range, an excessive increase in the viscosity of the solvent is prevented when the enzyme solution is added and stirred and mixed in the <Method for producing a granule> described below, and it is easier to sufficiently support laccase on the support.

[0025] The granules of the present embodiment may contain a cationic substance from the viewpoint of further improving storage stability. The cationic substance is preferably a cationic substance capable of forming a metal cation, and Cu 2+ The inclusion of a cationic substance in the granules improves the thermal stability of the granules and makes it difficult for the enzymatic activity of the laccase to decrease, thereby further improving the storage stability.

[0026] The granulated product of this embodiment may further contain a binder to facilitate granulation. The binder may be gum arabic, polyvinyl alcohol, sodium alginate, gelatin, cellulose, etc. The amount of the binder is usually 0 to 30 parts by mass, and may be 10 to 20 parts by mass, relative to 100 parts by mass of the support.

[0027] The granulated product of the present embodiment may contain a compound having a phenolic hydroxyl group (sometimes referred to as a "phenolic compound" in the present specification).

[0028] The phenolic compound used in this embodiment is not particularly limited as long as it has one or more phenolic hydroxyl groups in one molecule, although phenolic compounds having two or more phenolic hydroxyl groups in one molecule tend to have a stronger deodorizing effect.

[0029] The phenolic compound may be either a natural product or a non-natural product. The non-natural product may be, for example, a chemically synthesized product or may be obtained by chemically treating a natural product (e.g., chemical modification, decomposition, etc.).

[0030] More specific examples of phenolic compounds include tannic acid; ferulic acid; catechins (catechin and catechin derivatives) such as (+)-catechin, (-)-catechin, (+)-gallocatechin, (-)-catechin gallate, (+)-gallocatechin gallate, (-)-epicatechin, (-)-epigallocatechin, (-)-epicatechin gallate, and (-)-epigallocatechin gallate; lignosulfonates such as calcium lignosulfonate, sodium lignosulfonate, magnesium lignosulfonate, and ammonium lignosulfonate; gallic acid (also known as 3,4,5-trihydroxybenzoic acid); propyl gallate (also known as propyl 3,4,5-trihydroxybenzoate); pyrogallol; coffee bean extract components such as chlorogenic acid; grape seed extract components; and components contained in green tea extract. More specifically, examples of the coffee bean extract component, grape seed extract component, or green tea extract-containing component include polyphenols. The structural formulas of some of these phenolic compounds are shown below. Note that chlorogenic acid is a general term for multiple types of compounds that share a common skeleton, and there are multiple types of compounds other than the compounds shown below.

[0031] [ka]

[0032] [ka]

[0033] [ka]

[0034] In the present specification, when a structure in which one or more hydrogen atoms in a particular compound are substituted with a group other than a hydrogen atom is assumed, a compound having such a substituted structure is referred to as a "derivative" of the particular compound. In this specification, unless otherwise specified, the term "group" includes not only an atomic group formed by bonding multiple atoms but also a single atom.

[0035] Among phenolic compounds, tannic acid, ferulic acid, catechins, lignin sulfonates, gallic acid, propyl gallate, coffee bean extract components, grape seed extract components, and green tea extract components are advantageous in that they can achieve a high deodorizing effect even when the amount of laccase used in the composition is reduced. Furthermore, among these phenolic compounds, tannic acid, catechins, propyl gallate, coffee bean extract components, grape seed extract components, and green tea extract components are more preferred in that they can achieve a high deodorizing effect in a shorter period of time.

[0036] The phenolic compound used in the granules of this embodiment may be one type only, or two or more types, and when two or more types are used, the combination and ratio thereof can be adjusted as desired.

[0037] The phenolic compound used in the granules of this embodiment preferably contains at least one selected from the group consisting of tannic acid, ferulic acid, catechins, lignin sulfonates, gallic acid, propyl gallate, coffee bean extract components, grape seed extract components, and green tea extract-containing components, and may contain, for example, at least one selected from the group consisting of tannic acid, ferulic acid, catechin, and calcium lignin sulfonate. The composition of the present embodiment more preferably contains, as the phenolic compound, at least one selected from the group consisting of tannic acid, catechins, propyl gallate, coffee bean extract components, grape seed extract components, and green tea extract-containing components, and may contain, for example, at least one selected from the group consisting of tannic acid and catechin.

[0038] The ratio of the enzyme solution content to the phenolic compound content used in the granulated product of this embodiment ([enzyme solution content (parts by mass)] / [phenolic compound content (parts by mass)]×100) is preferably 30% by mass to 1000% by mass, and may be, for example, 30% by mass to 700% by mass, 30% by mass to 500% by mass, 60% by mass to 1000% by mass, 90% by mass to 1000% by mass, or 60% by mass to 700% by mass. When the ratio is equal to or greater than the lower limit, the deodorizing effect of the granulated product of this embodiment is enhanced. When the ratio is equal to or less than the upper limit, a high deodorizing effect can be obtained with a lower laccase content.

[0039] The granulated product of the present embodiment may contain hydrophilic inorganic fine particles as the other component (1). Hydrophilic inorganic fine particles are water-insoluble particles containing a hydrophilic inorganic substance as a main component. Hydrophilic inorganic fine particles usually contain 50 mass% or more of the hydrophilic inorganic substance based on the total mass of the particles. The hydrophilic inorganic substance preferably contains silicon (Si) as an element, and examples thereof include hydrophilic silicon dioxide, calcium silicate hydrate, and aluminum silicate.

[0040] The average particle size of the hydrophilic inorganic fine particles can be 150 μm or less. When the average particle size of the hydrophilic inorganic fine particles is 150 μm or less, the storage stability of the granulated product can be further improved. As described above, the surface of the core of the granulated product of this embodiment has fine irregularities. Therefore, hydrophilic inorganic fine particles with small particle diameters can easily enter the recesses on the surface of the core. The average particle diameter of the hydrophilic inorganic fine particles can be 100 μm or less, or even 50 μm or less. There is no particular lower limit on the average particle diameter, but from the viewpoints that nano-sized fine particles are expensive and difficult to handle because they are absorbed into the human body through the skin surface, a particle diameter of 0.1 μm or more is preferable.

[0041] The pore volume of the hydrophilic inorganic fine particles can be 0.5 mL / g or more. When the pore volume of the hydrophilic inorganic fine particles is 0.5 mL / g, the storage stability of the granulated product can be improved.

[0042] When a phenolic compound is absorbed into hydrophilic inorganic microparticles, the contact area between the phenolic compound and the supported laccase is reduced, which is thought to result in improved storage stability. Hydrophilic inorganic microparticles that have an average particle size of 150 μm or less and a pore volume of 0.5 mL / g or more are particularly effective in improving storage stability. The upper limit of the pore volume is not particularly limited, but can be, for example, 10 mL / g or less. In the present invention, the pore volume is defined as a value measured by nitrogen adsorption or mercury porosimetry. Therefore, it is sufficient that the pore volume measured by at least one of the nitrogen adsorption and mercury porosimetry methods is within the above-mentioned numerical range.

[0043] The inorganic fine particles exemplified above can be produced by a conventional method, or can be obtained by appropriately selecting from commercially available products.

[0044] The other component (1) contained in the granulated product of this embodiment may be one type only, or two or more types, and when there are two or more types, the combination and ratio thereof can be adjusted as desired.

[0045] As the granulated product of this embodiment, the granulated products of the following first to fifth embodiments are preferred. Hereinafter, one embodiment of the granulated product according to the present invention will be described with reference to the drawings.

[0046] First Embodiment The granulated product of the first embodiment is shown in Figure 1. Figure 1 shows a schematic cross-sectional view of a granulated product 10 of the first embodiment. The granulated product 10 includes a porous support 11 and laccase 12 supported on the porous support 11. The granulated material 10 of the first embodiment is preferably a granulated material obtained by stirring and granulating a porous support 11 and a laccase 12. A method for producing the granulated material obtained by stirring and granulating will be described later in <Method for producing granulated material>.

[0047] Second Embodiment The granulated material of the second embodiment includes a porous support, and laccase and a phenolic compound supported on the support. 2(A) shows a schematic cross-sectional view of a granulated material 20 according to the second embodiment. The granulated material 20 includes a porous support 11, and a laccase 12 and a phenolic compound 13 supported on the porous support.

[0048] The granulated material 20 of the second embodiment is preferably a granulated material obtained by stirring and granulating a porous support 11, a laccase 12, and a phenolic compound 13. A method for producing the stirred and granulated material will be described later in <Method for producing granulated material>.

[0049] Third Embodiment The granulated material of the third embodiment includes a porous support 11, the granulated material 10 of the first embodiment supported on the porous support, and a phenolic compound 13 supported on the porous support. 2(B) shows a schematic cross-sectional view of a granulated material 30 according to the third embodiment. The granulated material 30 includes a porous support 11, the granulated material 10 according to the first embodiment supported on the porous support 11, and a phenolic compound 13 supported on the porous support 11.

[0050] The granulated material of the third embodiment preferably has a granulated material obtained by stirring and granulating a porous support 11, the granulated material 10 of the first embodiment, and a phenolic compound 13. A method for producing the granulated material obtained by stirring and granulating will be described later in <Method for producing granulated material>.

[0051] The granulated product of the second embodiment described above can be produced more easily than the granulated product of the third embodiment in that granulation only needs to be performed once. On the other hand, the granules of the third embodiment described above have higher storage stability than the granules of the second embodiment, since the contact area between the laccase and the phenolic compound is small.

[0052] Fourth Embodiment The granulated product of the fourth embodiment contains the granulated product of the first embodiment and a phenolic compound, and the phenolic compound adheres to at least a portion of the surface of the granulated product of the first embodiment. 3(A) shows a schematic cross-sectional view of a granulated material 40 of the fourth embodiment. The granulated material 40 contains the granulated material 10 of the first embodiment and a phenolic compound 13, and the phenolic compound 13 adheres to at least a portion of the surface of the granulated material 10 of the first embodiment.

[0053] Fifth Embodiment The granulated material of the fifth embodiment comprises the granulated material of the first embodiment, a phenolic compound, and hydrophilic inorganic particles, and the phenolic compound and hydrophilic inorganic particles adhere to at least a portion of the surface of the granulated material of the first embodiment. 3(B) shows a schematic cross-sectional view of a granulated material 50 of the fifth embodiment. The granulated material 50 contains the granulated material 10 of the first embodiment, a phenolic compound 13, and hydrophilic inorganic particles 51, and the phenolic compound 13 and the hydrophilic inorganic particles 51 are attached to at least a portion of the surface of the granulated material 10 of the first embodiment.

[0054] <Method of manufacturing granules> The granulated product of the present embodiment can be produced by appropriately using a known method. In particular, when producing granules using agitation granulation, a known agitation mixer equipped with an agitation blade, a scraper, etc. can be used. The agitation mixer preferably has a vertical uniaxial mixer configuration. Specific examples of such a mixer include Super Mixer SMP-2 (manufactured by Kawata Corporation), Intensive Mixer EL1 (manufactured by Nippon Eirich Co., Ltd.), and Triple Master TMG-1 (manufactured by Shinagawa Kogyosho Co., Ltd.).

[0055] When the granulated product of this embodiment is produced by agitation granulation, it can be produced, for example, in the following order of steps A to C.

[0056] [Step A] First, the porous support is placed in a stirring mixer and stirred for a predetermined time. The stirring time in step A can be 5 to 15 minutes. The stirring speed can be 3 to 8 m / sec.

[0057] [Step B] The enzyme solution is added and stirred and mixed for a predetermined period of time. The stirring time in step B can be 30 seconds to 5 minutes. The stirring speed in step B can be gradually increased from 1 m / s to 5 m / s to 15 m / s to 30 m / s. The solvent used for the enzyme solution is not particularly limited, but may be a sodium phosphate buffer or a Tris-HCl buffer, and may also contain other components (1) such as polyhydric alcohols. When the solvent contains a polyhydric alcohol such as glycerin, the content of the polyhydric alcohol such as glycerin in the enzyme solution ([polyhydric alcohol content (parts by mass)] / [amount of enzyme solution (parts by mass)]×100) is preferably 22% by mass to 39% by mass, more preferably 27% by mass to 34% by mass. When the content of the polyhydric alcohol such as glycerin is equal to or greater than the lower limit of the above range, the effect of improving the water retention capacity of the granulated product is more easily exerted. On the other hand, when the content of the polyhydric alcohol such as glycerin is equal to or less than the upper limit of the above range, an excessive increase in the viscosity of the solvent is prevented when the enzyme solution is added and stirred, making it easier to sufficiently support laccase on the support.

[0058] [Step C] Further, when the material is stirred for a predetermined time, the material is wetted with the enzyme solution and aggregates to form a roughly spherical core. The stirring time in step C can be 30 seconds to 5 minutes. The stirring speed in step C can be 3 m / s to 15 m / s.

[0059] In other words, when producing the granulated material of this embodiment using stirring granulation, the method for producing a granulated material can be said to include step A in which a porous support is added and stirred and mixed, step B in which an enzyme solution is added and mixed after step A, and step C in which the mixture obtained in step B is stirred and granulated to form particles.

[0060] The above steps may be performed using the same stirring mixer, or some steps may be performed using different stirring mixers. For example, step A is a dry powder mixing process, so it may be performed using a container rotary mixer. Step B is preferably performed using a uniaxial mixer.

[0061] Alternatively, in step A, a phenolic compound is added in addition to the porous support, thereby producing the granulated material of the second embodiment.

[0062] Alternatively, the granulated product of the first embodiment produced by steps A to C can be produced by again adding a porous support and a phenolic compound in step A, and adding distilled water instead of the enzyme solution in step B, thereby producing the granulated product of the third embodiment.

[0063] Furthermore, by carrying out the following step D, the granulated product of the fourth embodiment can be produced.

[0064] Step D The phenolic compound can be added to the granules of this embodiment in a stirring mixer and stirred for a predetermined time, thereby coating at least a portion of the surface of the granules with the phenolic compound. The stirring time in step D can be 30 seconds to 2 minutes. The stirring speed in step D can be 3 m / s to 8 m / s. Step D may be carried out in the same stirring mixer as steps A to C, or in a stirring mixer different from that used in steps A to C, but is preferably carried out in a uniaxial mixer.

[0065] Alternatively, in step D, hydrophilic inorganic fine particles are added in addition to the phenolic compound, thereby producing the granulated product of the fifth embodiment.

[0066] <Composition> The composition of the present embodiment contains the granulated product of the present embodiment and a phenolic compound.

[0067] <Phenol compounds> The phenolic compound used in the composition of the present embodiment may be the same as the phenolic compounds exemplified in the above-mentioned other component (1), and is preferably at least one selected from the group consisting of tannic acid, ferulic acid, catechins, lignin sulfonates, gallic acid, propyl gallate, coffee bean extract components, grape seed extract components, and green tea extract-containing components.

[0068] The shape of the phenolic compound used in the composition of this embodiment is not particularly limited, and may be a powder or granules. Among granules, granules having a uniform particle size distribution are preferred from the viewpoint that the uniformity of the entire composition is improved. The granulation method is not particularly limited, and may be stirring granulation or pressure granulation.

[0069] The ratio of the content of the enzyme solution to the content of the phenolic compound used in the composition of this embodiment ([content of enzyme solution (parts by mass)] / [content of phenolic compound (parts by mass)]×100) is preferably 100% by mass to 1000% by mass, and may be, for example, 100% by mass to 700% by mass, 100% by mass to 500% by mass, 200% by mass to 1000% by mass, or 300% by mass to 1000% by mass, or 200% by mass to 700% by mass. When the ratio is equal to or greater than the lower limit, the deodorizing effect of the composition of this embodiment is enhanced. When the ratio is equal to or less than the upper limit, a high deodorizing effect can be obtained with a smaller laccase content.

[0070] Other ingredients The composition of the present embodiment may contain the granule of the present embodiment and other components (sometimes referred to herein as "other components (2)") other than the phenolic compound, within the scope of not impairing the effects of the present invention. The other components (2) can be selected arbitrarily depending on the purpose and are not particularly limited. The composition of the present embodiment may contain the above-mentioned other component (1).

[0071] The composition of the present embodiment may contain a support as another component (2). The support may be any particle capable of supporting a phenolic compound. Usually, the phenolic compound is supported on the support by impregnating the support with the phenolic compound. The support may be, for example, one or more selected from the porous support, particles mainly composed of cellulose such as wood flour and crystalline cellulose, and inorganic particles such as silica.

[0072] As the composition of this embodiment, the composition of the following sixth embodiment is preferred. Hereinafter, one embodiment of the composition according to the present invention will be described with reference to the drawings.

[0073] Sixth Embodiment The composition of the sixth embodiment includes the granule of the first embodiment, and a granule containing a carrier and the phenolic compound. FIG. 4 is a schematic cross-sectional view of the granulated material 10 of the first embodiment and a granulated material 60 contained in a composition 70 of the sixth embodiment. The granulated material 60 is a granulated material containing a support 61 and a phenolic compound 13 supported on the support 61.

[0074] The granulated material 60 used in the sixth embodiment is preferably a granulated material obtained by stirring and granulating the support 61 and the phenolic compound 13 supported on the support 61.

[0075] The granulated material 10 and the granulated material 60 used in the sixth embodiment can also be used as a kit containing the granulated material 10 and the granulated material 60.

[0076] While the preferred embodiments of the present invention have been described above with reference to the drawings, it goes without saying that the present invention is not limited to the above-described embodiments. The forms of the components shown in the above-described embodiments are merely examples, and various modifications can be made based on design requirements, etc., without departing from the spirit of the present invention. For example, the compositions of the respective embodiments can be appropriately blended.

[0077] <Method of producing the composition> The composition of the present embodiment can be produced by appropriately selecting a known method. In particular, when a composition is produced by agitation granulation, a stirring mixer similar to that described in the method for producing a granulated product of this embodiment can be used. The composition of the sixth embodiment can be produced by using a phenolic compound instead of laccase to produce a granulated material containing the phenolic compound in the order of steps A to C described above, and then mixing it with the granulated material of this embodiment.

[0078] <How to deodorize malodorous components> Malodorous components can be deodorized by contacting the granules or composition of this embodiment with the malodorous components. In order to deodorize malodorous components, the object to be brought into contact with the granules or composition may consist of only the malodorous components, or may be a mixture of the malodorous components and other components (sometimes referred to as "other components (3)" in this specification), and may be in any of liquid, gaseous, and solid forms.

[0079] When the granulated material or composition of this embodiment is used, it is presumed that the laccase in the granulated material of this embodiment acts on phenolic compounds, converting the phenolic compounds into active species, and these active species react with malodorous components, converting the malodorous components into other components, thereby exerting a deodorizing effect.

[0080] Examples of malodorous components include nitrogen-containing compounds (compounds having a nitrogen atom) such as amines (primary amines, secondary amines, tertiary amines), ammonia, urea, indole, and indole derivatives; sulfur-containing compounds (compounds having a sulfur atom) such as mercaptans, hydrogen sulfide, and sulfides; however, malodorous components are not limited to these.

[0081] The amount of the granules or composition used during deodorization is not particularly limited, as long as the amounts of laccase and phenolic compound are such that the desired degree of deodorization can be achieved.

[0082] During deodorization, it is preferable to use water as the other component (3) and contact the granules or composition with malodorous components in the presence of water. By performing deodorization in the presence of water, the action of laccase on phenolic compounds as described above and the reaction between the active species of phenolic compounds generated by this action and the malodorous components proceed more smoothly, resulting in faster deodorization of the malodorous components. This is presumably because the use of water increases the solubility of the various raw materials or reaction intermediates used during deodorization.

[0083] When the granules or composition are brought into contact with the malodorous component in the presence of water, a mixture of water and the malodorous component may be used in advance. The mixture may be, for example, an aqueous solution, a liquid water-containing substance such as an aqueous dispersion, or a solid water-containing substance. The aqueous solution may be, for example, a body fluid such as urine.

[0084] The amount of water used as the other component (3) during deodorization is preferably 500 to 3,000 times by mass, and more preferably 700 to 2,100 times by mass, relative to the phenolic compounds in the composition. When the total amount of water is equal to or greater than the lower limit, the effect obtained by using water is enhanced. When the total amount of water is equal to or less than the upper limit, excessive use of water is suppressed. [Example]

[0085] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0086] (Evaluation of laccase enzymatic activity) The enzymatic activity of the crude laccase enzyme solution used in this example was evaluated as follows. First, ABTS was added as a substrate to a 50 mM sodium citrate buffer solution (pH 3.0) and dissolved therein to prepare an ABTS solution with a concentration of 10 mM. 100 μL of the ABTS solution was mixed with 2840 μL of a 50 mM sodium citrate buffer solution (pH 3.0), and the resulting mixture was kept at 40°C. Next, 60 μL of the laccase crude enzyme solution was added to this warmed mixture to obtain 3 mL of reaction solution.

[0087] The absorbance of the resulting reaction solution was measured at a wavelength of 420 nm for 1 minute. The increase in absorbance at a wavelength of 420 nm, ΔA 420 The reaction time (min) was calculated from the above and the enzyme activity (U / mL) of laccase was calculated according to the formula (i) and was found to be 140 U / mL.

[0088] [Example 1] In Example 1, a porous support and laccase were stirred and granulated to produce granules having a phenolic compound attached to at least a portion of the surface of the resulting particles.

[0089] (Preparation of granulated material) Step A 30.0 parts by mass of bentonite (manufactured by Hojun Co., Ltd.) was charged into a stirring mixer and stirred and mixed at 7.0 m / sec.

[0090] Step B Next, 6.6 parts by mass of the laccase crude enzyme solution was added to the agitator mixer and stirred at 15.0 m / sec. After that, it was confirmed that there were no lumps or clumps in the wet powder, and Step B was completed.

[0091] Step C Next, the wet powder was stirred and mixed at 5.0 m / sec. After that, it was visually confirmed that the particles had aggregated into a spherical shape, and Step C was completed.

[0092] Through steps A to C, 36.6 parts by mass of a stirred granule containing laccase supported on bentonite was obtained.

[0093] Step D The stirred granules obtained in Steps A to C were mixed with tannic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) by stirring. After that, it was confirmed that there was no more tannic acid scattering, and Step D was completed. Step D yielded a granule in which tannic acid adhered to at least a portion of the surface of the granule (Granule 1).

[0094] [Example 2] In Example 2, a granulated product was produced by stirring and granulating a porous support and laccase.

[0095] In Example 1, except that tannic acid was not mixed with granulated material 1, i.e., steps up to step C were carried out and step D was not carried out, the same procedure as in Example 1 was used to obtain 36.6 parts by mass of granulated material in which laccase was supported by bentonite (granulated material 2). Next, the obtained granulated product 2 was allowed to stand at 4°C for 4 weeks.

[0096] [Example 3] In Example 3, a granulated product was prepared by stirring and granulating a porous support and laccase, and a granulated product was prepared by stirring and granulating a porous support and a phenolic compound.

[0097] Granulated product 2 was obtained in the same manner as in Example 2. The resulting stirred granulated product was then allowed to stand at 4°C for 4 weeks.

[0098] Next, 38.1 parts by mass of granules in which tannic acid was supported on bentonite were obtained in the same manner as in Example 2, except that 1.5 parts by mass of tannic acid and 6.6 parts by mass of distilled water were added instead of the laccase crude enzyme solution (granules 3).

[0099] [Example 4] In Example 4, a granulated product was produced by stirring and granulating a porous support, laccase, and a phenolic compound.

[0100] In Example 1, except that tannic acid was added and mixed in step A instead of step D, i.e., 1.5 parts by mass of tannic acid was added and stirred and mixed in step A, and steps up to C were carried out, and step D was not carried out, the same procedure as in Example 1 was followed to obtain 38.1 parts by mass of a granulated product in which laccase was supported on bentonite (granulated product 4). Next, the obtained granulated product 4 was allowed to stand at 4°C for 4 weeks.

[0101] [Example 5] In Example 5, a granulated product was prepared by stirring and granulating a porous support and laccase, and a granulated product was prepared by stirring and granulating a porous support and a phenolic compound.

[0102] Granules 2 were obtained in the same manner as in Example 2. Next, in step A described in Example 1, 15.0 parts by mass of granulated material 2, 10.0 parts by mass of bentonite, and 0.6 parts by mass of tannic acid were added and stirred and mixed instead of 30.0 parts by mass of bentonite, and in step B, 2.7 parts by mass of distilled water were added and stirred and mixed instead of the laccase crude enzyme solution, and step C was then performed to obtain 28.3 parts by mass of granulated material 2 and tannic acid supported by bentonite (granulated material 5). Next, the obtained granules 5 were allowed to stand at 4°C for 4 weeks.

[0103] [Example 6] In Example 6, a granulated product was prepared by stirring and granulating a porous support and laccase, and then attaching a phenolic compound and hydrophilic inorganic particles to the surface of the granulated product.

[0104] Granulated product 6 was obtained in the same manner as in Example 1, except that Silopage 720 (Fuji Silysia Chemical Ltd.) was added in step D. That is, after obtaining granulated product 2:36.6 parts by mass of laccase-supported bentonite, tannic acid and Silopage 720 were stirred and mixed, and then step D was completed after confirming that no tannic acid or Silopage 720 had scattered. Step D resulted in a granulated product in which tannic acid and Silopage 720 adhered to at least a portion of the surface of the granulated product (granulated product 6). Next, the obtained granules 6 were allowed to stand at 4°C for 4 weeks.

[0105] [Example 7] In Example 7, a granulated product was produced by stirring and granulating a porous support, laccase, and glycerin.

[0106] In Example 2, a laccase crude enzyme solution containing 30% by mass of glycerin was used instead of the laccase crude enzyme solution, and the same procedure as in Example 2 was repeated to obtain 36.6 parts by mass of a granulated product in which laccase was supported on bentonite (granulated product 7). Next, the obtained granules 7 were allowed to stand at 40°C for 3 weeks.

[0107] [Comparative Example 1] In Comparative Example 1, a liquid agent to be used for granulation, that is, a mixed liquid of laccase and a phenolic compound, was prepared.

[0108] At room temperature, 300 μL of laccase crude enzyme solution was added to 1 mg of tannic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and stirred for 5 minutes to obtain the liquid used in step B of granulation preparation, i.e., a mixture of laccase and phenolic compounds.

[0109] Comparative Example 2 In Comparative Example 2, a granulated product was produced by stirring and granulating non-porous cellulose powder and laccase.

[0110] In Example 1, 9.8 parts by mass of non-porous cellulose powder (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 4.2 parts by mass of sodium carboxymethylcellulose (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) were used instead of bentonite, and tannic acid was not mixed in. In other words, cellulose powder and sodium carboxymethylcellulose were used instead of bentonite, and steps up to C were carried out, and step D was not carried out. The same procedure as in Example 1 was repeated to obtain 23.0 parts by mass of a granule in which laccase was supported by cellulose powder (granule 8). Next, the obtained granules 8 were allowed to stand at 4°C for 4 weeks.

[0111] Comparative Example 3 A granulated product of bentonite (granulated product 9) was obtained in the same manner as in Example 1, except that the laccase crude enzyme solution and tannic acid were not added.

[0112] [Test Example 1] 30 μL of a 15% by mass aqueous solution of methyl mercaptan sodium (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 20 mL of distilled water and stirred to obtain a diluted aqueous solution of methyl mercaptan sodium. Using the obtained diluted aqueous solution of methyl mercaptan sodium, the concentration of malodorous components (sulfur-containing compounds) in the gas generated from it was measured using the measurement method described below, and it was previously confirmed that the measured value was approximately 30 ppm by volume.

[0113] 1800 μL of distilled water and 200 μL of a diluted aqueous solution of sodium methyl mercaptan were added to a 50 mL vial, the opening of the vial was sealed with parafilm, and the contents of the vial were stirred in this state at a temperature of 25° C. Then, 10 minutes after the start of stirring, the concentration of malodorous components (sulfur-containing compounds) contained in the gas in the headspace region inside the vial was measured using a gas detector tube (manufactured by Gastec Corporation).

[0114] The deodorizing rate of the malodorous components was calculated using the following formula (iii). The results are shown in Table 1. (Deodorization rate of malodorous components (%)) = 100 × {1 - (measured value of concentration of sulfur-containing compounds in gas when granulated material is used) / (measured value of concentration of sulfur-containing compounds in gas when granulated material is not used)} (iii) In the formula (iii), the "measured value of the concentration of sulfur-containing compounds in the gas when a granulated material is used" is the measured value of the concentration of sulfur-containing compounds in this example, and the "measured value of the concentration of sulfur-containing compounds in the gas when a granulated material is not used" is the measured value of the concentration of sulfur-containing compounds in Test Example 1. In other words, the deodorizing rate in Test Example 1 is 0%.

[0115] [Observation of the surface of granulated material] The surface of the prepared granules 2 was observed at 40x magnification using a microscope VHX-7000 (manufactured by Keyence Corporation). The results are shown in Figures 5 and 6. Figure 6 is a diagram in which the surface irregularities of Figure 5 are displayed in shades of color. The higher the height, the lighter the color, and the lower the height, the darker the color. As shown in Figures 5 and 6, it was confirmed that the surface of the granules produced by stirring and mixing has fine irregularities. From this, it is speculated that the surface area of ​​granules produced by stirring and mixing tends to be large, and water, the trigger component for the deodorizing effect, can easily penetrate into the recesses on the surface of the granules, which makes it easier for the laccase held inside the porous material to come into contact with water, which tends to improve the deodorizing effect.

[0116] [Evaluation of deodorizing effect] The deodorizing effects of the granules and solvents obtained in Examples 1 to 8 and Comparative Examples 1 to 3 were evaluated. Example 1 The concentration of malodorous components was measured in the same manner as in Test Example 1, except that 2.0 mL of distilled water and 0.5 g of the granules obtained above were added instead of 1800 μL of distilled water.

[0117] Example 2 The deodorizing performance was evaluated in the same manner as in Example 1, except that 0.5 g of granulated material 2, which had been left to stand for 4 weeks at 4°C, and 1 mg of tannic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added instead of 0.5 g of granulated material 1. The results are shown in Table 1.

[0118] Example 3 The deodorizing performance was evaluated in the same manner as in Example 1, except that 0.25 g of granulated material 2 and 0.25 g of granulated material 3 were added instead of 0.5 g of granulated material 1. The results are shown in Table 1.

[0119] Example 4 The deodorizing performance was evaluated in the same manner as in Example 1, except that 0.5 g of granulated material 4 that had been left to stand for 4 weeks at 4°C was added instead of 0.5 g of granulated material 1. The results are shown in Table 1.

[0120] Example 5 The deodorizing performance was evaluated in the same manner as in Example 1, except that 0.5 g of granulated material 5 that had been left to stand for 4 weeks at 4°C was added instead of 0.5 g of granulated material 1. The results are shown in Table 1.

[0121] Example 6 The deodorizing performance was evaluated in the same manner as in Example 1, except that 0.5 g of granulated material 6 that had been left to stand for 4 weeks at 4°C was added instead of 0.5 g of granulated material 1. The results are shown in Table 1.

[0122] Example 7 The deodorizing performance was evaluated in the same manner as in Example 1, except that 0.5 g of Granulated Product 1 was replaced with 0.5 g of Granulated Product 7 that had been left to stand for 3 weeks at 40°C and 1 mg of tannic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The results are shown in Table 1.

[0123] Example 8 The deodorizing performance was evaluated in the same manner as in Example 1, except that 0.5 g of granulated material 2, which had been left to stand for 3 weeks at 40°C, and 1 mg of tannic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added instead of 0.5 g of granulated material 1. The results are shown in Table 1.

[0124] (Comparative Example 1) The deodorizing performance was evaluated in the same manner as in Test Example 1, except that 1.50 mL of distilled water and the total amount of the mixed solution of laccase and phenolic compound were added instead of 1800 μL of distilled water. The results are shown in Table 1.

[0125] (Comparative Example 2) The deodorizing performance was evaluated in the same manner as in Example 1, except that 0.5 g of granulated product 8 that had been left to stand for 4 weeks at 4°C and 1 mg of tannic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added instead of 0.5 g of granulated product 1. The results are shown in Table 1.

[0126] (Comparative Example 3) The deodorizing performance was evaluated in the same manner as in Example 1, except that granule 9 was added instead of 0.5 g of granule 1. The results are shown in Table 1.

[0127] [Table 1]

[0128] As shown in Table 1, the composition of this embodiment achieved a deodorizing rate of 80% or more of malodorous components within 10 minutes of applying the composition to a diluted aqueous solution of sodium methyl mercaptan in Examples 1 to 8. This demonstrates that the composition of this embodiment exhibits a high deodorizing effect in a short period of time and also has high storage stability.

[0129] Furthermore, granulated material 2 (Examples 2 and 3), granulated material 4 (Example 4), granulated material 5 (Example 5), and granulated material 6 (Example 6), which were each left to stand for 4 weeks at 4°C, achieved a deodorizing rate of 100% for malodorous components, the same as granulated material 1 (Example 1), which was not left to stand for 4 weeks at 4°C. From this, it was revealed that the granulated material comprising a porous support and laccase supported on the porous support (granulated material of the first embodiment), the granulated material comprising a porous support and laccase and a phenolic compound supported on the porous support (granulated material of the second embodiment), the granulated material comprising a porous support, the granulated material of the first embodiment supported on the porous support, and a phenolic compound (granulated material of the third embodiment), and the granulated material of the first embodiment, a phenolic compound, and hydrophilic inorganic particles, in which the phenolic compound and hydrophilic inorganic particles adhere to at least a portion of the granulated material of the first embodiment (granulated material of the fifth embodiment) all have high storage stability.

[0130] Furthermore, granulated material 2 (Example 8) left to stand for 3 weeks at 40°C had a deodorizing rate of 80% for malodorous components, whereas granulated material 7 (Example 7) left to stand for 3 weeks at 40°C had a deodorizing rate of 100% for malodorous components. This confirmed that when a granulated material containing a porous support and laccase supported on the porous support contains a polyhydric alcohol such as glycerin, the water retention of the granulated material is improved and the enzymatic activity of the laccase is less likely to decrease, resulting in higher storage stability.

[0131] Furthermore, granule 8 (Comparative Example 2), which contained non-porous cellulose powder and laccase supported on the non-porous cellulose powder, had a deodorizing rate of 40% for malodorous components, whereas granule 2 (Example 2), which contained a porous support and laccase supported on the porous support, had a deodorizing rate of 100% for malodorous components. This confirms that when a porous support is used in the granules, the laccase is supported within the pores of the support, reducing contact with moisture and other substances in the environment, making it less susceptible to the effects of the surrounding environment and improving the storage stability of the laccase. Granule 9 (Comparative Example 3), which contained only a porous support, had a deodorizing rate of 0% for malodorous components, so the deodorizing effect of the porous support alone was not confirmed in this Example. [Explanation of symbols]

[0132] 10... granulated material, 11... porous support, 12... laccase, 13... phenolic compound, 20... granulated material, 30... granulated material, 40... granulated material, 50... granulated material, 51... hydrophilic inorganic particles, 60... granulated material, 61... support, 70... composition [Industrial Applicability]

[0133] According to the present invention, it is possible to provide a granulated product that has a high deodorizing effect while also having excellent storage stability and flowability, a composition using said granulated product, and a method for deodorizing malodorous components using said granulated product or said composition.

Claims

1. A granulated product comprising a porous support and laccase supported on the porous support.

2. The granulated product according to claim 1, which is a granulated product obtained by stirring and granulating the porous support and the laccase.

3. The granule according to claim 1 or 2, further comprising a compound having a phenolic hydroxyl group.

4. The granules according to claim 3, comprising a compound having a phenolic hydroxyl group supported on the porous support.

5. A granulated product according to claim 3, wherein a compound having a phenolic hydroxyl group is attached to at least a portion of the surface of the granules obtained by stirring and granulating the porous support and the laccase.

6. A granulated material as described in claim 3, wherein a compound having a phenolic hydroxyl group and hydrophilic inorganic microparticles are attached to at least a portion of the surface of the granules obtained by stirring and granulating the porous support and the laccase.

7. The granule according to claim 3, wherein the compound having a phenolic hydroxyl group is at least one selected from the group consisting of tannic acid, ferulic acid, catechins, lignin sulfonates, gallic acid, propyl gallate, coffee bean extract components, grape seed extract components, and green tea extract-containing components.

8. The granule according to claim 1 or 2, further comprising a polyhydric alcohol.

9. The granulated product according to claim 8, wherein the polyhydric alcohol is glycerin.

10. A composition comprising the granulated product according to claim 1 or 2 and a compound having a phenolic hydroxyl group.

11. A method for deodorizing a malodorous component, comprising contacting the granulated material according to claim 1 with the malodorous component to deodorize the malodorous component.

12. The method for deodorizing a malodorous component according to claim 11, wherein the granules are contacted with the malodorous component in the presence of water.

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