JP2010254909A - Deodorant composition - Google Patents

Abstract

An object of the present invention is to provide a deodorant composition containing a polypeptide, which has improved odor, particularly acetaldehyde adsorptivity.
A deodorant composition comprising (A) a polypeptide and (B) a polyhydroxyamine compound exhibits excellent acetaldehyde adsorptivity. The adsorbed composition is effectively adsorbed without being re-dissipated.
[Selection figure] None

Description

  The present invention relates to a deodorant composition containing a polypeptide and a polyhydroxyamine compound.

  In recent years, research has been conducted on filters (nonwoven fabrics) containing organic natural products such as chitosan and catechin (green tea polyphenol). By mixing these organic natural products with the fibers that make up the nonwoven fabric, or by attaching them to the fiber surface, functions such as deodorization, VOC adsorption, antibacterial / antifungal and antiviral properties are added. It is being adopted as a filter for an air purifier, a filter for an air conditioner, a filter for an automobile air conditioner, and the like. In such applications, adsorptivity of acetaldehyde, which is a bad odor mainly generated from tobacco and automobile exhaust gas, is required. In the case of chitosan and catechin, it easily reacts with formaldehyde (chemical adsorption) and exhibits high removal performance, but the removal performance of acetaldehyde tends to be somewhat inferior and there is room for improvement.

  In addition, a coating sheet containing leather powder (collagen) and fibers treated with a fiber treatment agent comprising a synthetic resin emulsion and a hydrophilic organic natural product fine powder (collagen) have been studied. There was room for improvement in terms of adsorptivity (see Patent Documents 1 and 2).

JP-A-5-69503 JP-A-6-10268

  That is, the problem to be solved by the present invention is to provide a deodorant composition having improved acetaldehyde adsorptivity in a deodorant composition containing a polypeptide.

  The present invention has the following configuration.

  1). A deodorant composition comprising (A) a polypeptide and (B) a polyhydroxyamine compound.

  2). (A) The deodorant composition according to 1), wherein the polypeptide is at least one selected from cross-linked collagen, collagen, silk, and eggshell membranes.

  3). (B) The polyhydroxyamine compound is 2-amino-2-hydroxymethyl-1,3-propanediol, 2-amino-2-hydroxyethyl-1,3-propanediol, 2-amino-2-methyl-1 1, 2-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-1,3-propanediol, and 1) or 2) Deodorant composition as described.

  4). (A) The polypeptide is cross-linked collagen, and is regenerated collagen cross-linked with a treatment liquid containing a monofunctional epoxy compound and / or a metal salt, according to any one of 1) to 3) Deodorant composition.

  5). 4. The deodorant composition according to 4), wherein the metal salt is an aluminum salt.

  6). Deodorant fiber containing the deodorant composition in any one of 1) -5).

  7). A nonwoven fabric containing the deodorant composition according to any one of 1) to 5).

  8). The deodorizing filter using the nonwoven fabric as described in 7).

  The deodorant composition of the present invention is excellent in acetaldehyde adsorptivity.

  The present invention is described in detail below.

  The deodorant composition of the present invention is a deodorant composition comprising (A) a polypeptide and (B) a polyhydroxyamine compound.

  As the polypeptide (A) of the present invention, cross-linked collagen, collagen, silk, eggshell membranes are preferably used. Among them, a regenerated collagen which is a crosslinked collagen and is crosslinked with a treatment liquid containing a monofunctional epoxy compound and / or a metal salt is preferable because of its high thermal stability and good water resistance.

  The regenerated collagen will be described below.

In the following description, a regenerated collagen fiber and a method for producing regenerated collagen powder by pulverization of the regenerated collagen fiber are described, but the production method is not limited thereto.
The regenerated collagen of the present invention is produced by producing a solubilized collagen solution from animal skin, bones, tendons and the like, followed by crosslinking treatment. In particular, it has the feature that thorough purification of collagen and precise cross-linking are possible.

  As a method for producing the collagen, for example, as disclosed in Japanese Patent Application Laid-Open No. 2002-249882, it is preferable to use a portion of the skin as a raw material. Examples of the floor skin include a fresh floor skin obtained from animals such as cows, pigs, horses, deer, sea breams, birds, fish, and salted raw skin. Most of these skins consist of insoluble collagen fibers, but there are impurities such as lipids such as glycerides, phospholipids and free fatty acids, proteins other than collagen such as glycoproteins and albumins, so these impurities are removed beforehand. It is preferable to keep it. For example, a leather treatment that is generally performed such as acid / alkali treatment, enzyme treatment, solvent treatment, etc. may be applied.

  The insoluble collagen that has been treated as described above is subjected to a solubilization treatment in order to cleave the cross-linked peptide portion. As a solubilization method, a publicly-known publicly known alkali solubilization method, enzyme solubilization method, or the like can be applied. As an improved method of the conventionally known alkali solubilization method, a method described in Japanese Examined Patent Publication No. 46-15033 may be used. As the enzyme solubilization method, for example, the methods described in JP-B-43-25829, JP-B-43-27513 and the like can be employed. Further, an alkali solubilization method and an enzyme solubilization method may be used in combination.

  When the solubilized collagen is further subjected to operations such as pH adjustment, salting out, water washing and solvent treatment, it is possible to obtain collagen with excellent quality and the like, and therefore it is preferable to perform these treatments. . The solubilized collagen obtained has an acidity adjusted to pH 2 to 4.5 with an acid such as hydrochloric acid, acetic acid or lactic acid so as to be a stock solution having a predetermined concentration of, for example, 1 to 15% by weight, preferably about 2 to 10% by weight. Dissolved using solution.

  In addition, you may perform filtration for the degassing | defoaming under pressure reduction stirring and the removal of a water-insoluble part as needed to the obtained collagen aqueous solution. In addition, stabilizers for the purpose of improving mechanical strength, improving water resistance and heat resistance, improving glossiness, improving spinnability, preventing coloration, preserving and the like, additives such as water-soluble polymer compounds, as necessary May be blended in an appropriate amount.

  Regenerated collagen fibers are formed by discharging the solubilized collagen aqueous solution into the inorganic salt aqueous solution through, for example, a spinning nozzle or slit. As the inorganic salt aqueous solution, for example, an aqueous solution of a water-soluble inorganic salt such as sodium sulfate, sodium chloride, or ammonium sulfate is used, and the concentration of these inorganic salts is usually adjusted to 10 to 40% by weight. The pH of the inorganic salt aqueous solution is usually 2 to 13, preferably 4 to 12, by adding a metal salt such as sodium borate or sodium acetate, hydrochloric acid, boric acid, acetic acid, sodium hydroxide, or the like. It is preferable to adjust.

  If the pH is too high or too low, the peptide bond of collagen tends to be subject to hydrolysis, and the desired regenerated collagen tends to be difficult to obtain. Further, the temperature of the inorganic salt aqueous solution is not particularly limited, but it is usually preferably 35 ° C. or lower. When the temperature is higher than 35 ° C., the soluble collagen is denatured, so that the strength is lowered and stable production becomes difficult. In addition, although the minimum of temperature is not specifically limited, Usually, it can adjust suitably according to the solubility of inorganic salt.

  The free amino group of the collagen is preferably cross-linked by reacting with a monofunctional epoxy compound. When a monofunctional epoxy compound is used, there is little coloring and water resistance becomes favorable.

  Examples of the monofunctional epoxy compound include ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, styrene oxide, epichlorohydrin, epibromohydrin, glycidyl methyl ether, butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, Examples thereof include glycidyl ethers such as polyethylene oxide glycidyl ether, glycidyl esters such as glycidyl formate, glycidyl acetate, glycidyl acrylate, glycidyl methacrylate, and glycidyl benzoate, and glycidyl amides. In view of reactivity and ease of treatment after the reaction, it is preferable to treat with epichlorohydrin.

  The modification rate of the free amino group can be measured by amino acid analysis, and calculated based on the amino acid analysis value of the collagen fiber before the crosslinking reaction or the known composition of the free amino acid constituting the collagen used as a raw material. Can do. The modification rate of the free amino group of the regenerated collagen is preferably 50% or more, more preferably 65% or more, and still more preferably 80% or more. When the modification rate is low, it is difficult to obtain good characteristics due to heat resistance.

The regenerated collagen is preferably crosslinked by dipping in an aqueous solution of a metal salt. As a metal salt used for crosslinking, an aluminum salt, a chromium salt, a zirconium salt, or a titanium salt can be used. Among them, an aluminum salt or a zirconium salt is preferable because it is not colored and has good water resistance. In particular, an aluminum salt is preferable. As the aluminum salt aqueous aluminum salt solution, the following _{formula, Al (OH) n Cl 3} -n, or _{Al 2 (OH) 2n (SO} 4) in _3-n (wherein, n is 0.5 to 2. 5). Basic aluminum chloride or basic aluminum sulfate represented by formula (5) is preferred. Specifically, for example, aluminum sulfate, aluminum chloride, alum or the like is used. These aluminum can be used individually or in mixture of 2 or more types.

  The metal salt concentration of the aqueous metal salt solution is preferably 0.3 to 5% by weight in terms of the metal oxide. If the concentration of the metal salt is low, the content of the metal salt in the regenerated collagen is low, the water resistance is insufficient, and if it is high, it becomes hard after treatment and the texture is impaired.

  The pH of the aqueous metal salt solution is usually preferably adjusted to 2.5 to 5 using, for example, hydrochloric acid, sulfuric acid, acetic acid, sodium hydroxide, sodium carbonate or the like. If the pH is too low, the collagen structure tends to be broken and denatured. If the pH is too high, precipitation of the metal salt occurs, making it difficult to penetrate.

  Although the liquid temperature of metal salt aqueous solution is not specifically limited, 50 degreeC or less is preferable. When this liquid temperature exceeds 50 ° C., collagen tends to be denatured.

  The time for immersing the collagen in the aqueous metal salt solution is preferably 3 hours or more, and more preferably 4 to 25 hours. If this immersion time is short, the reaction of the metal salt is difficult to proceed, and the water resistance of the collagen becomes insufficient. Moreover, although there is no restriction | limiting in particular in the upper limit of immersion time, if too long, processing time will take and it will become economically disadvantageous. Usually, the reaction of the metal salt proceeds sufficiently within 25 hours, and the water resistance becomes good. In addition, an inorganic salt such as sodium chloride, sodium sulfate, or potassium chloride may be appropriately added to the aqueous solution of the metal salt so that the metal salt is not rapidly absorbed into the collagen to cause uneven concentration.

  The regenerated collagen thus treated with a metal salt and cross-linked is then washed with water, oiled and dried. Moreover, a pigment, dye, a filler, a flame retardant, antioxidant, a light stabilizer etc. can also be added as needed.

  The regenerated collagen fiber obtained by the above method can be pulverized to obtain a regenerated collagen powder.

  The regenerated collagen fiber can be chopped (coarse pulverized) to a fiber length suitable for pulverization, and the chopped product can be further pulverized, or the fiber can be directly pulverized. For chopping (coarse pulverization), for example, a rotary blade cutter, a belt cutter, a shearing machine, a cutter mill or the like can be used, and chopping can be performed to about 0.1 mm to several mm.

  Furthermore, the pulverized regenerated collagen fibers are pulverized into ball mills (dry, wet), jet mills, vibration mills, centrifugal (CF) mills, roller mills, rod mills, pin mills, planetary ball mills, grinder mills, etc. Finer powder can be obtained by finely pulverizing with the use of. When using a ball mill, it is preferable to use alumina or zirconia as the ball material in terms of hardness.

  Depending on the type of pulverizer and the pulverization time, the particle diameter of the obtained regenerated collagen powder can be appropriately adjusted. For example, when a vibration mill is used, the average particle diameter is 5 to 1 hour to several tens of hours. About 80 μm can be obtained. Moreover, when obtaining a thing with an average particle diameter of 0.01-10 micrometers, you may classify the pulverized regenerated collagen powder further.

  The average particle size of the regenerated collagen powder is preferably 0.01 to 80 μm, and more preferably 1 to 20 μm. If it is too large, the deodorization rate decreases, which is not preferable. If it is too small, dispersibility in water or an organic solvent is lowered, which is not preferable. The average particle diameter can be determined by, for example, a microtrack method which is one of laser diffraction / scattering methods.

  Examples of (B) polyhydroxyamine compounds include 2-amino-2-hydroxymethyl-1,3-propanediol, 2-amino-2-hydroxyethyl-1,3-propanediol, and 2-amino-2- Methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-1,3-propanediol, 4-amino-4-hydroxypropyl-1,7-heptanediol 2- (N-ethyl) amino-1,3-propanediol, 2- (N-ethyl) amino-2-hydroxymethyl-1,3-propanediol, 2- (N-decyl) amino-1,3 -Propanediol, 2- (N-decyl) amino-2-hydroxymethyl-1,3-propanediol and the like.

  Among these, from the viewpoint of deodorizing performance, 2-amino-2-hydroxymethyl-1,3-propanediol, 2-amino-2-hydroxyethyl-1,3-propanediol, 2-amino-2-methyl It is preferable to use -1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-1,3-propanediol and the like.

  An acid salt neutralized with an inorganic acid or organic acid of a polyhydroxyamine compound can also be used, but the deodorizing performance may be lowered, and it is preferable to use a polyhydroxyamine compound containing no inorganic acid or organic acid. . Examples of the acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, fatty acids having 1 to 12 carbon atoms, and alkyl sulfuric acids having 1 to 3 carbon atoms.

  Said polyhydroxyamine compound can be used individually or in mixture of 2 or more types. The polyhydroxyamine compound can be produced by a conventional method. The polyhydroxyamine compound has the effect of increasing the dispersibility of the polypeptide powder in a solvent, particularly water. For example, regenerated collagen powder is difficult to disperse in water alone, but finely disperses well in an aqueous solution containing a polyhydroxyamine compound.

  The polypeptide can be used as a solution or a dispersion. These solutions or dispersions and a polyhydroxyamine compound can be mixed to form the composition of the present invention. As the solvent, water or an aqueous solution containing an inorganic salt is preferable. A water-soluble organic solvent such as methanol, ethanol, acetone or the like may be used in combination.

  Examples of the shape of the deodorant composition of the present invention include, but are not limited to, solutions, dispersions, powders, fibers, nonwoven fabrics, coating films, and films.

As a manufacturing method of the fiber containing the deodorant composition of the present invention, for example,
There is a method of treating a fiber made of (A) a polypeptide with an aqueous solution containing (B) a polyhydroxyamine compound. Also,
There is a method in which (A) a solution or dispersion containing a polypeptide and (B) a polyhydroxyamine compound are mixed to form a fiber or treat the fiber. As the treatment method, a known method can be used. For example, there is a method in which the fiber is taken out, and then the fiber is taken out, drained, and dried.

  The immersion time is 30 minutes or more, more preferably 1 hour or more. If it is 30 minutes or more, adhesion to the surface and penetration into the fiber will be sufficient. Moreover, you may drain liquid using a mangle. Moreover, it is preferable that a drying temperature is 100 degrees C or less. If the temperature exceeds 100 ° C., the polypeptide tends to be thermally deteriorated, which is not preferable. Moreover, it can replace with immersion and a spray method can also be employ | adopted.

  As a manufacturing method of the nonwoven fabric containing the deodorant composition of this invention, there exists a method of processing nonwoven fabrics, such as polyester, with the composition containing (A) polypeptide and (B) polyhydroxyamine compound, for example. Moreover, after processing a nonwoven fabric with polypeptide, there exists the method of immersing in the crosslinking liquid containing a metal salt, bridge | crosslinking, and also processing with a polyhydroxyamine compound.

  As a method for producing a powder containing the deodorant composition of the present invention, for example, there is a method in which a fiber comprising (A) a polypeptide is treated with (B) a polyhydroxyamine compound and then pulverized into a powder. .

  Alternatively, (A) a powder containing a polypeptide can be treated with (B) a polyhydroxyamine compound to obtain a powder.

  The deodorant composition of the present invention is excellent in acetaldehyde adsorptivity. In addition, it has a feature that the acetaldehyde once adsorbed is released again, so-called re-emission property is low. Furthermore, it has high adsorptivity to formaldehyde, ammonia, trimethylamine, acetic acid, isovaleric acid and the like.

  The deodorant composition of the present invention and the fibers and non-woven fabrics containing the deodorant composition are used and used as deodorant filters for air purifiers, deodorant filters for indoor air conditioners, and automobile air conditioners. Examples include deodorant filters, air elements, oil filters, automobile seats, automobile interior materials, sofas, curtains, carpets, wallpaper, clothing, protective clothing, deodorant fibers, masks, paper diapers, and sanitary products.

  Hereinafter, the present invention will be described more specifically with reference to examples. In addition, this invention is not limited at all by these Examples.

(Production Example 1) Method for Producing Regenerated Collagen Fiber-A After adding 30 g of hydrogen peroxide aqueous solution diluted to 30% by weight to skin of 1200 kg (collagen content: 180 kg) using cow's floor skin as a raw material, A stock solution was prepared by dissolving in a lactic acid aqueous solution and adjusting the pH to 3.5 and the solid content to 7.5% by weight. The stock solution was stirred and defoamed with a stirring defoamer (Dalton Co., Ltd., 8DMV type) under reduced pressure, transferred to a piston-type spinning stock solution tank, and allowed to stand under reduced pressure for defoaming.

  This stock solution is extruded by a piston, and then is fed in a fixed amount by a gear pump, filtered through a sintered filter having a pore diameter of 10 μm, passed through a spinning nozzle having a pore diameter of 0.275 mm, a hole length of 0.5 mm, and a hole number of 300, and sodium sulfate 20 % Was discharged at a spinning speed of 5 m / min into a 25 ° C. coagulation bath (adjusted to pH 11 with boric acid and sodium hydroxide).

  Next, the obtained regenerated collagen fibers (300 fibers, 20 m) were added to 1.32 kg of an aqueous solution containing 1.7% by weight of epichlorohydrin, 0.0246% by weight of sodium hydroxide, and 17% by weight of sodium sulfate. After soaking at 25 ° C. for 4 hours, the temperature of the reaction solution was further raised to 43 ° C. and impregnated for 2 hours.

  After the reaction was completed, the reaction solution was removed, and then washed with water three times using 1.32 kg of 25 ° C. water in a fluid type apparatus. Thereafter, it was impregnated with 1.32 kg of an aqueous solution containing 5% by weight of aluminum sulfate, 0.9% by weight of trisodium citrate, and 1.2% by weight of sodium hydroxide at 30 ° C. After 5 hours and 4 hours, 13.2 g of a 5% by weight aqueous sodium hydroxide solution was added to the reaction solution, respectively, and reacted for a total of 6 hours. After the reaction was completed, the reaction solution was removed, and then washed with water three times using 1.32 kg of 25 ° C. water in a fluid type apparatus.

  Subsequently, a part of the produced fiber was immersed in a bath filled with an oil agent made of a pluronic polyether-based antistatic agent to adhere the oil agent. One end of the fiber bundle is fixed inside a hot air convection dryer set to 50 ° C., a weight of 2.8 g is suspended from one fiber at the other end, and dried under tension for 2 hours, 60 dtex Regenerated collagen fibers were obtained.

Production Example 2 Production Method of Regenerated Collagen Powder-A Regenerated collagen powder-A was prepared by physically pulverizing the regenerated collagen fiber-A shown in Production Example 1. That is, first, 30 kg of regenerated collagen fibers are shredded to a length of about 1 mm with a cutter mill SF-8 (manufactured by Sanriki Manufacturing Co., Ltd.) and recovered using a cyclone CYC-600 type (manufactured by Sanriki Manufacturing Co., Ltd.). did.

Next, grinding was performed using a vibration mill FV-100 (manufactured by Chuo Kako Co., Ltd.). The same alumina balls (diameter 20 mm) were placed in an alumina container having a capacity of 283 L so as to have a filling capacity of 80% and the chopped collagen fibers to a filling capacity of 50 kg, and pulverization was carried out for 24 hours. As a result, a powder having an average particle diameter (50% diameter) of 11.0 μm was obtained. Using this dry powder classifier micron separator MS-1H (manufactured by Hosokawa Micron Corporation) and a pulse jet type dust collector CP-16-6 (manufactured by Hosokawa Micron Corporation), the air volume is 12 m ³ / min (secondary air volume ³ m ³ / min). The powder was classified at a rotational speed of 5000 rpm to obtain a powder having an average particle size of 5.0 μm (hereinafter referred to as regenerated collagen powder-A). The particle size of the powder was measured by a wet laser diffraction / scattering method. Microtrac MT3300 (Nikkiso Co., Ltd.) was used and methanol was used as a dispersion medium.

Example 1
A 2-amino-2-hydroxymethyl-1,3-propanediol aqueous solution was prepared according to the formulation (parts by weight) shown in Table 1, and the regenerated collagen fiber-A was immersed for 1 hour. After taking out the fiber from the aqueous solution and thoroughly squeezing out the water, it was dried in an oven at 80 ° C. for 1 hour to obtain a fiber containing a deodorant composition. The weight change rate before and after the aqueous solution treatment (= weight of fiber after treatment / weight of fiber before treatment) was 1.08.

(Example 2)
Fibers containing the deodorant composition were obtained in the same manner as in Example 1 with the blending ratio (parts by weight) shown in Table 1. The weight change rate before and after the aqueous solution treatment was 1.02.

(Example 3)
A fiber containing a deodorant composition in the same manner as in Example 1 except that the polyhydroxyamine compound was changed to 2-amino-2-methyl-1,3-propanediol by the formulation (parts by weight) shown in Table 1. Got. The weight change rate before and after the aqueous solution treatment was 1.07.

(Comparative Examples 1-2)
Regenerated collagen fiber-A and 2-amino-2-hydroxymethyl-1,3-propanediol (granular) were used as samples.

(1) Acetaldehyde adsorptivity of fiber and polyhydroxyamine Measured by bag method. A fiber or polyhydroxyamine (granular) 0.5 g was placed in a 3 L capacity Tedlar bag (Omi Odo Air Service Co., Ltd.) and heat sealed, and then 1.5 L of nitrogen was injected. A methanol solution of acetaldehyde was added so that the acetaldehyde concentration was 10 ppm. The concentration of acetaldehyde after 72 hours was measured using a gas detector tube No. It measured using 92L (made by Gastec Co., Ltd.).

(2) Re-emission (acetaldehyde)
The regenerated collagen fibers that had been evaluated for acetaldehyde adsorptivity by the above method were taken out of the Tedlar bag, put in another Tedlar bag, heat sealed, and then injected with 1.5 L of nitrogen. In an oven set at 60 ° C., after heating for 1 hour, the concentration of acetaldehyde released again from the fiber was measured using the gas detector tube No. It measured using 92L (made by Gastec Co., Ltd.).

  Examples 1 to 3 are fibers containing regenerated collagen and polyhydroxyamine. Excellent acetaldehyde adsorptivity. Moreover, there was no re-emission property and it was favorable. Comparative Example 1 is a regenerated collagen fiber not treated with an aqueous polyhydroxyamine solution. Acetaldehyde adsorptivity is insufficient. Comparative Example 2 is polyhydroxyamine (granular). Acetaldehyde adsorptivity is insufficient.

Example 4
A treatment liquid containing regenerated collagen powder and polyhydroxyamine was prepared according to the formulation (parts by weight) shown in Table 2. After 30 g of this treatment liquid was immersed in 1.0 g (250 cm ² ) of PET / polyolefin non-woven fabric AL040TCJ (manufactured by Venus Paper Co., Ltd., basis weight 40 g / m ² ), the water was squeezed out well, and then in an oven at 80 ° C. It dried for 1 hour and obtained the nonwoven fabric containing a deodorant composition. The weight change rate before and after the aqueous solution treatment (= the weight of the nonwoven fabric after the treatment / the weight of the nonwoven fabric before the treatment) was 1.31.

(Example 5)
In the same manner as in Example 4, except that the base non-woven fabric was changed to 1.0 g (500 cm ² ) of rayon fiber non-woven fabric 3020 (manufactured by Venus Paper Co., Ltd., basis weight 20 g / m ² ) according to the formulation (parts by weight) shown in Table 2. A nonwoven fabric containing an odorous composition was obtained. The weight change rate before and after the aqueous solution treatment was 1.29.

(Example 6)
A nonwoven fabric containing a deodorant composition was obtained in the same manner as in Example 4 with the blending ratio (parts by weight) shown in Table 2. The weight change rate before and after the aqueous solution treatment was 1.30.

(Example 7)
A nonwoven fabric containing a deodorant composition in the same manner as in Example 4 except that the polyhydroxyamine compound was changed to 2-amino-2-methyl-1,3-propanediol by the formulation (parts by weight) shown in Table 2 Got. The weight change rate before and after the aqueous solution treatment was 1.27.

(Example 8)
A deodorant composition is contained in the same manner as in Example 4 except that Vinetex S-200L (manufactured by Daiwa Chemical Industry Co., Ltd., silicone resin) is added as a binder resin by blending (parts by weight) shown in Table 2. A nonwoven fabric was obtained. The weight change rate before and after the aqueous solution treatment was 1.28.

Example 9
A nonwoven fabric was obtained in the same manner as in Example 4 except that silk powder (average particle size 6.2 μm) was used as a polypeptide according to the formulation (parts by weight) shown in Table 2. The weight change rate before and after the aqueous solution treatment was 1.23.

(Comparative Examples 3-4)
A nonwoven fabric was obtained in the same manner as in Example 4 with the formulation (parts by weight) shown in Table 2. The weight change rates before and after the aqueous solution treatment were 1.23 and 1.29, respectively.

(Comparative Example 5)
A PET / polyolefin nonwoven fabric AL040TCJ (manufactured by Venus Paper Co., Ltd., basis weight 40 g / m ² ) was used as a sample.

(3) Acetaldehyde adsorptivity of nonwoven fabric Measured by bag method. A non-woven fabric of 250 cm ² was put into a 3 L capacity Tedlar bag and heat sealed, and then 1.5 L of nitrogen was injected. A methanol solution of acetaldehyde was added so that the acetaldehyde concentration was 10 ppm. The concentration of acetaldehyde after 24 hours was measured using a gas detector tube No. It measured using 92L (made by Gastec Co., Ltd.).

(4) Dispersibility of polypeptide powder The appearance of the treatment liquid was visually determined. ○: Almost no aggregated particles are observed. Δ: A small amount of aggregated particles is confirmed. X: Many agglomerated particles are confirmed.

  Examples 4 to 9 are nonwoven fabrics treated with a treatment liquid containing polypeptide powder and polyhydroxyamine. Excellent acetaldehyde adsorptivity. Moreover, the dispersibility of the polypeptide powder in the aqueous solution was also good.

  Comparative Example 3 is a nonwoven fabric treated with polypeptide powder. Acetaldehyde adsorptivity is low, and dispersibility of the polypeptide powder is also low. Comparative Example 4 is a nonwoven fabric treated with a polyhydroxyamine compound. Low acetaldehyde adsorptivity. Comparative Example 5 is a base nonwoven fabric (PET / polyolefin type). Low acetaldehyde adsorptivity.

(5) Formaldehyde adsorption property of fiber It measured by the bag method. After putting 0.5 g of fiber into a 3 L capacity Tedlar bag and heat-sealing, 1.5 L of nitrogen was injected. A methanol solution of formaldehyde was added so that the formaldehyde concentration was 20 ppm. The formaldehyde concentration after 24 hours was measured with the gas detector tube No. It measured using 91 (made by Gastec Co., Ltd.).

(6) Re-emission (formaldehyde)
The regenerated collagen fibers that had been evaluated for formaldehyde adsorption by the above method were taken out of the Tedlar bag, put into another Tedlar bag, heat sealed, and then injected with 1.5 L of nitrogen. After placing in an oven set at 60 ° C. and heating for 1 hour, the concentration of formaldehyde released again from the fiber was measured using the gas detector tube No. It measured using 91 (made by Gastec Co., Ltd.).

  Example 1 is a regenerated collagen fiber containing the deodorant composition of the present invention. Excellent formaldehyde adsorption. Moreover, re-emission property was not seen but it was favorable. Comparative Example 1 is a regenerated collagen fiber. Insufficient formaldehyde adsorption and re-emission properties were observed.

(Production Example 3) Method for Producing Collagen Aqueous Solution for Non-woven Fabric Treatment After charging 30 g of hydrogen peroxide aqueous solution diluted to 30% by weight into 1200 kg (collagen content: 180 kg) of cow's floor skin solubilized with alkali A stock solution was prepared by dissolving in an aqueous lactic acid solution and adjusting the pH to 3.5 and the solid content to 7.5% by weight. The stock solution was stirred and defoamed with a stirring defoamer (Dalton Co., Ltd., 8DMV type) under reduced pressure, transferred to a piston-type spinning stock solution tank, and allowed to stand under reduced pressure for defoaming. What was diluted with water and adjusted to solid content concentration 0.18 wt% was made into the collagen aqueous solution for nonwoven fabric processing.

(Production Example 4) Method for producing aluminum cross-linking liquid To 942 ml of water, 10 g of sodium citrate, 33.2 ml of 25% aqueous sodium hydroxide solution, 90.5 g of aluminum sulfate and 159.75 g of sodium sulfate are added, and stirred well, and the aluminum cross-linking liquid It was.

(Example 10)
The base nonwoven fabric was coated with an aluminum-crosslinked collagen insoluble material by the following method and then treated with polyhydroxyamine to produce a nonwoven fabric containing a deodorant composition. That is, PET / polyolefin non-woven fabric AL040TCJ (manufactured by Venus Paper Co., Ltd., basis weight 40 g / m ² ) was immersed in the collagen aqueous solution of Production Example 3 and shaken at room temperature for 1 hour. Soaked. After standing at room temperature overnight, it was washed with a sufficient amount of water, and then the nonwoven fabric was air-dried. The weight change rate was 1.06. Further, after immersing in 5 wt% 2-amino-2-hydroxymethyl-1,3-propanediol aqueous solution and thoroughly squeezing out moisture, it is dried in an oven at 80 ° C. for 1 hour and contains a deodorant composition. A nonwoven fabric was obtained. The weight change rate before and after the aqueous solution treatment was 1.13.

The acetaldehyde adsorptivity of the nonwoven fabric was measured by the bag method. A non-woven fabric of 250 cm ² was put into a 3 L capacity Tedlar bag and heat sealed, and then 1.5 L of nitrogen was injected. A methanol solution of acetaldehyde was added so that the acetaldehyde concentration was 10 ppm. The concentration of acetaldehyde after 24 hours was measured using a gas detector tube No. As a result of measuring using 92L (made by Gastec Co., Ltd.), the acetaldehyde concentration was less than 0.2 ppm.

Claims (8)

  A deodorant composition comprising (A) a polypeptide and (B) a polyhydroxyamine compound.   The deodorant composition according to claim 1, wherein the polypeptide (A) is at least one selected from cross-linked collagen, collagen, silk, and eggshell membranes.   (B) The polyhydroxyamine compound is 2-amino-2-hydroxymethyl-1,3-propanediol, 2-amino-2-hydroxyethyl-1,3-propanediol, 2-amino-2-methyl-1 3 or 3 propanediol, 2-amino-2-ethyl-1,3-propanediol, or 2-amino-1,3-propanediol. Deodorant composition as described.   The (A) polypeptide is cross-linked collagen, and is regenerated collagen cross-linked with a treatment liquid containing a monofunctional epoxy compound and / or a metal salt. Deodorant composition.   The deodorant composition according to claim 4, wherein the metal salt is an aluminum salt.   Deodorant fiber containing the deodorant composition in any one of Claims 1-5.   The nonwoven fabric containing the deodorizing composition in any one of Claims 1-5.   A deodorizing filter using the nonwoven fabric according to claim 7.