JP5140011B2 - Method for reducing basic malodorous substances - Google Patents

Description

  The present invention relates to a method for reducing basic malodorous substances and a package.

  The smell is a factor that greatly affects the taste, smell, nerves, and the like. If it smells good, you can relax and increase your appetite. Conversely, if it smells bad (hereinafter also referred to as “bad odor”), it may be dangerous, memory may decline, concentration may be impaired, and discomfort may be caused. In general, since an odor substance develops an odor that can be detected by the nose even at a very low concentration, countermeasures against bad odors are a major problem.

  Examples of substances that cause bad odors (hereinafter also referred to as “malodorous substances”) include basic malodorous substances, neutral malodorous substances, and acidic malodorous substances. Examples of basic malodorous substances include ammonia generated from manure, pets, sweat, socks and the like, trimethylamine, methylamine, ethylamine and the like generated from raw garbage, sewage, fishing rods and the like. Neutral substances include ethyl mercaptan generated from raw garbage, feces, sewage, etc., acetaldehyde generated from cigarettes, acetaldehyde generated from tobacco, etc., hexanal generated from old rice, xylene generated from chemical factories, etc. , Toluene and the like. Acid malodorous substances include hydrogen sulfide generated from feces, sewage, pets, etc., methyl mercaptan generated from garbage, sewage, pets, etc., isovaleric acid generated from sweat, socks, pets, feces, sewage, pets, etc. Scatol generated from Among these, ammonia, trimethylamine, hydrogen sulfide and methyl mercaptan are said to be four major malodorous substances.

Various methods have been proposed for reducing these malodorous substances.
For example, Patent Document 1 discloses a two-component type odor that can deodorize mixed malodors containing at least two or more of sulfur-containing compounds, aldehydes, lower fatty acids, amines, and the like. Odorants are listed.

Patent Document 2 describes a deodorizing composition for human and animal excrement, which contains an acid agent and a water-soluble polymer.
Patent Document 3 describes a deodorant water-absorbing resin obtained by adding a carboxylic acid such as maleic acid, succinic acid, or phthalic acid having low water solubility to a water-absorbing resin.

  However, these methods are those using low molecular weight substances as deodorant components, and using high molecular weight substances as deodorant components, and a method that can easily and efficiently reduce malodorous substances is Not yet developed.

JP 2007-252543 A JP-T-2001-507970 JP-A-9-108317

  The present invention is a method that can easily and efficiently reduce basic malodorous substances among malodorous substances, and an object thereof is to provide a method for reducing basic malodorous substances using a high molecular weight substance as a deodorizing component. And

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that basic malodorous substances can be reduced by contacting basic malodorous substances with a specific high molecular weight substance and water, The present invention has been completed.

That is, the basic malodorous substance reducing method of the present invention is characterized by bringing polyglycolic acid, water, and a basic malodorous substance into contact with each other.
In addition, the basic malodorous substance reducing method of the present invention is characterized in that a deodorant containing polyglycolic acid as a deodorizing component, water, and a basic malodorous substance are brought into contact with each other. The form of the deodorant is preferably a film, a pellet, a package, a powder, a fiber, or a fabric.

  The package of the present invention is formed from a package and contents, and by placing the contents generating a basic malodorous substance in a package made of a film containing at least polyglycolic acid, and performing sealed packaging can get. The content is preferably food.

  According to the present invention, basic malodorous substances can be reduced easily and efficiently. Moreover, the package formed from the package which consists of a film containing polyglycolic acid, and the content can reduce the basic malodorous substance generated from the said content significantly.

FIG. 1 is a graph showing changes with time in ammonia concentration in Example 1 and Comparative Examples 1 and 2. FIG. 2 is a graph showing changes with time in trimethylamine concentration in Example 2 and Comparative Examples 3 to 4. FIG. 3 is a graph showing the change over time in the trimethylamine concentration in Example 3 and Comparative Examples 5-6. FIG. 4 is a graph showing changes with time in triethylamine concentration in Example 4 and Comparative Examples 7 to 8. FIG. 5 is a graph showing the change with time of triethylamine concentration in Comparative Examples 9 to 11. FIG. 6 is a schematic diagram showing the configuration of the inner bag and the outer bag in Example 5 and Comparative Examples 12-13. FIG. 7 is a graph showing changes over time in ammonia concentration in Examples 6 and 7.

Next, the method for reducing the basic malodorous substance of the present invention will be specifically described.
The basic malodorous substance reducing method of the present invention is characterized by bringing polyglycolic acid, water, and a basic malodorous substance into contact with each other.

In addition, the basic malodorous substance reducing method of the present invention is characterized in that a deodorant containing polyglycolic acid as a deodorizing component, water, and a basic malodorous substance are brought into contact with each other.
The method of reducing the basic malodorous substance of the present invention using a high molecular weight substance, that is, polyglycolic acid, as the deodorant component is more effective than the method using a low molecular weight substance as the deodorant component. The method and the like are simple, and it is possible to efficiently reduce odorous substances drifting over a wide area such as gaseous odorous substances for a long period of time.

(Polyglycolic acid)
The polyglycolic acid used in the present invention is a homopolymer or copolymer having a repeating unit represented by the following general formula (1).

ポリグリコール酸が単独重合体の場合、上記一般式（１）で表される繰り返し単位の含有割合は１００質量％となる。

When the polyglycolic acid is a homopolymer, the content of the repeating unit represented by the general formula (1) is 100% by mass.

  When the polyglycolic acid is a copolymer, the content of the repeating unit represented by the general formula (1) is preferably 60% by mass or more, and more preferably 70% by mass or more. It is especially preferable that it is 80 mass% or more. If the content of the repeating unit represented by the general formula (1) in the polyglycolic acid is too low, the crystallinity tends to be lowered, and the barrier property of the package formed from the polyglycolic acid is impaired. And stability may be impaired.

  The polyglycolic acid used in the present invention is usually a crystalline polymer having a melting point. Such polyglycolic acid can be produced, for example, by a method of polycondensing glycolic acid, glycolic acid alkyl ester, or glycolate. Polyglycolic acid can also be produced by ring-opening polymerization of glycolide.

  Such polycondensation or ring-opening polymerization can be carried out by a known method, and is not particularly limited, but is usually carried out in the presence of a catalyst. The type of the catalyst is not particularly limited. For example, tin compounds such as tin halides (for example, tin dichloride and tin tetrachloride) and organic carboxylates (for example, tin octoate and tin octylate); alkoxy titanates And titanium compounds such as alkoxyaluminum; zirconium compounds such as zirconium acetylacetone; antimony compounds such as antimony halide and antimony oxide;

  In order to produce a copolymer of glycolic acid as polyglycolic acid, monomers such as glycolide or glycolic acid and various comonomers are copolymerized. Examples of the comonomer include lactide, lactones (for example, β-propiolactone, β-butyrolactone, pivalolactone, γ-butyrolactone, δ-valerolactone, β-methyl-δ-valerolactone, ε-caprolactone), trimethylene. Cyclic monomers such as carbonate and 1,3-dioxane; hydroxycarboxylic acids such as lactic acid, 3-hydroxypropanoic acid, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid and 6-hydroxycaproic acid or alkyl esters thereof; ethylene glycol; Mention may be made of a substantially equimolar mixture of an aliphatic diol such as 1,4-butanediol and an aliphatic dicarboxylic acid such as succinic acid or adipic acid or an alkyl ester thereof. These comonomers may be used individually by 1 type, and may be used in mixture of 2 or more types.

  Among these comonomers, cyclic monomers such as lactide, caprolactone, and trimethylene carbonate; hydroxycarboxylic acids such as lactic acid, and the like are preferable because they are easily copolymerized and a copolymer having excellent physical properties can be easily obtained. When glycolide is used as a raw material for polyglycolic acid, it is preferable to use a cyclic monomer such as lactide, caprolactone, trimethylene carbonate as a comonomer. Glycolide and the cyclic monomer can be easily subjected to ring-opening copolymerization. Preferable examples of the polyglycolic acid copolymer include a copolymer of glycolide and lactide, a copolymer of glycolide and caprolactone, and the like. As the lactide, L-lactide is preferable from the viewpoint of availability. As caprolactone, ε-caprolactone is preferred.

  The comonomer is preferably 40% by mass or less in all raw materials. When the copolymerization ratio of the comonomer is increased, the crystallinity of polyglycolic acid is liable to be impaired, and the barrier property of the package formed from polyglycolic acid is impaired, or the stability is impaired. In order to further exhibit the effect of reducing the basic malodorous substance by polyglycolic acid, it is preferable to lower the crystallinity of polyglycolic acid. On the other hand, in order to maintain the physical properties required for the deodorizing form of the polyglycolic acid, such as the shape of the film, pellets, package or powder, and each deodorizing form, it may be preferable to increase crystallinity. In particular, it is preferable to increase the crystallinity in order to maintain the barrier property and shape of the film or package.

  Polyglycolic acid polymerization equipment includes various extruder-type equipment, vertical equipment with paddle blades, vertical equipment with helical ribbon blades, kneader-type horizontal equipment, ampoule-type equipment, and annular-type equipment. The device can be selected as appropriate.

  The polymerization temperature is a temperature within a range of 120 to 300 ° C., which is a substantial polymerization start temperature, and can be set according to the purpose. The polymerization temperature is preferably 130 to 250 ° C, more preferably 140 to 220 ° C, and particularly preferably 150 to 200 ° C. If the polymerization temperature is too high, the resulting polymer is susceptible to thermal decomposition. The polymerization time is in the range of 3 minutes to 20 hours, preferably 5 minutes to 18 hours. If the polymerization time is too short, the polymerization does not proceed sufficiently, and if it is too long, the resulting polymer tends to be colored.

  The weight average molecular weight (Mw) of the polyglycolic acid used in the present invention is usually 30,000 to 800,000, preferably 50,000 to 500,000. The number average molecular weight (Mn) of the polyglycolic acid used in the present invention is usually 10,000 to 800,000, preferably 16,000 to 500,000. In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values converted to polymethyl methacrylate by measurement by gel permeation chromatography (GPC) using a hexafluoroisopropanol solvent.

The polyglycolic acid used in the present invention has a melt viscosity measured at a temperature 20 ° C. higher than the melting point Tm (Tm + 20 ° C.) and a shear rate of 122 sec ⁻¹ , usually 100 to 10,000 Pa · s, preferably 200 to 8 000 Pa · s, more preferably 300 to 4,000 Pa · s.

  When such polyglycolic acid is brought into contact with a basic malodorous substance together with water, the basic malodorous substance can be efficiently reduced. The mechanism for reducing the basic malodorous substance is not clear, but the present inventors presume as follows. First, a part of polyglycolic acid is hydrolyzed by the action of water and a basic malodorous substance to produce a hydrolyzate. Next, it is estimated that the generated hydrolyzate may cause a chemical neutralization reaction with the basic malodorous substance, resulting in a reduction in the basic malodorous substance.

  Since the end of polyglycolic acid becomes a hydroxyl group and / or a carboxyl group at the time of synthesis, it exhibits hydrolyzability and is easily colored during melt processing. Therefore, normally, by adding a non-acid-forming OH group-capping agent and / or a carboxyl group-capping agent to polyglycolic acid, water resistance and hydrolyzability are improved, and coloring is suppressed.

  However, since the polyglycolic acid used in the present invention is desired to exhibit hydrolyzability as described above, it is preferable not to add a non-acid-forming OH group-capping agent and a carboxyl group-capping agent. On the other hand, as a deodorizing form of polyglycolic acid, in order to maintain the properties of films, pellets, packages or powders and the physical properties required for each deodorizing form, especially for maintaining the barrier properties and maintaining the shape of films and packages. In addition, a non-acid-forming OH group blocking agent and / or a carboxyl group blocking agent may be blended within a range that does not hinder the ability to reduce basic malodorous substances by polyglycolic acid.

  “Non-acid-forming” in a non-acid-forming OH group blocking agent means that a carboxyl group is not generated when the OH group remaining in the polyglycolic acid is bonded and sealed. Yes. As the non-acid-forming OH group sealing agent, diketene compounds, isocyanates and the like are used. Among these OH group blocking agents, diketene compounds are preferable from the viewpoint of reactivity. The OH group end capping agent is usually used in a proportion of 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of polyglycolic acid.

  As the carboxyl group blocking agent, a compound having a carboxyl group end blocking action and known as a water resistance improver for aliphatic polyesters can be used. Specific examples of the carboxyl group-capping agent include carbodiimide compounds such as N, N-2,6-diisopropylphenylcarbodiimide; 2,2′-m-phenylenebis (2-oxazoline), 2,2′-p. -Oxazoline compounds such as phenylenebis (2-oxazoline), 2-phenyl-2-oxazoline and styrene / isopropenyl-2-oxazoline; Oxazines such as 2-methoxy-5,6-dihydro-4H-1,3-oxazine Compounds; epoxy compounds such as N-glycidylphthalimide, cyclohexene oxide, tris (2,3-epoxypropyl) isocyanurate; and the like.

  Among these carboxyl group-capping agents, carbodiimide compounds are preferred, and any of aromatic, alicyclic, and aliphatic carbodiimide compounds are used, but aromatic carbodiimide compounds are particularly preferred, and those with particularly high purity are water resistant. Gives a stabilizing effect. The carboxyl group sealing agent is usually used in a proportion of 0.01 to 10 parts by mass, preferably 0.05 to 2.5 parts by mass with respect to 100 parts by mass of polyglycolic acid.

(water)
In the present invention, the form of water may be liquid or gaseous (water vapor). Moreover, the water | moisture content contained in the content containing a basic malodor substance may be sufficient.

(Basic malodorous substance)
The basic malodorous substance is preferably a substance selected from the group consisting of ammonium compounds and amines. Specific examples of the basic malodorous substance include ammonia, trimethylamine, methylamine, and ethylamine.

(Contact mode of each component)
The method for reducing basic malodorous substances of the present invention is a method in which polyglycolic acid, water, and basic malodorous substances are brought into contact with each other.

  The embodiment for contacting each component is not particularly limited as long as the basic malodorous substance can be reduced. For example, (i) an aspect in which a solid polyglycolic acid is brought into contact with an aqueous solution containing a basic malodorous substance, (Ii) an embodiment in which a solid polyglycolic acid is contacted with a gaseous or liquid basic malodorous substance in an atmosphere containing water vapor; (iii) a solid polyglycolic acid and liquid water; A mode in which a gaseous or liquid basic malodorous substance is brought into contact with the product, (iv) a basic malodorous substance via a solid polyglycolic acid and a material that transmits the basic malodorous substance, etc. A mode in which an aqueous solution is brought into contact, (v) a solid or polyglycolic acid and liquid water in contact with a material that permeates a basic malodorous substance, for example, a gas or liquid via a sealant of Such embodiments of contacting the base of malodorous substances.

  The contact temperature of each component is not particularly limited as long as water does not freeze, and is preferably 0 to 140 ° C, more preferably 0 to 100 ° C, and particularly preferably 0 to 60 ° C. preferable. When the contact temperature of each component is within the above range, basic malodorous substances can be efficiently reduced.

The amount of polyglycolic acid is not particularly limited as long as it can reduce the basic malodorous substance, but the repeating unit represented by the general formula (1) in polyglycolic acid is preferably 1 mol of basic malodorous substance. It is 10-10,000 mol, More preferably, it is 10-1,000 mol, More preferably, it is 10-100 mol. If the amount of polyglycolic acid is within the above range, basic malodorous substances can be efficiently reduced.
The amount of water is not particularly limited as long as it can reduce basic malodorous substances.

(Deodorants)
The deodorant used for this invention contains the polyglycolic acid mentioned above as a deodorizing component. Moreover, as a form of the said deodorizer, it is preferable that they are a film, a pellet, a package body, powder, a fiber, or a fabric. The package is preferably obtained from a film containing polyglycolic acid.

  When the deodorant is in the form of a film, pellet, or package, it may be a single layer or a multilayer. Hereinafter, the case where the form of the deodorizer is a powder or a single layer film, a single layer pellet, or a single layer package will be described.

  The deodorizer in the case of powder or single layer film, single layer pellet or single layer package preferably contains 70% by mass or more of the above polyglycolic acid, and 75% by mass or more. More preferably, it is more preferable to contain 80% by mass or more.

Moreover, the said deodorizer can mix | blend another thermoplastic resin, a heat stabilizer, and various additives as needed.
Other thermoplastic resins include, for example, polyolefin resins such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer; thermoplastic polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polystyrene, poly Polyaromatic vinyl resins such as α-methylstyrene; chlorine-containing resins such as polyvinyl chloride and polyvinylidene chloride; polyamide resins, polycarbonate resins, cyclic olefin resins, polyurethane resins, ethylene / vinyl alcohol copolymers (EVOH), Examples include other aliphatic polyester resins.

  The blending ratio of the other thermoplastic resin is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and further preferably 20 parts by mass or less with respect to 100 parts by mass of polyglycolic acid. When other thermoplastic resin is mix | blended within the said range, it is preferable at the point which improves adhesiveness with the base material to laminate | stack, or improves a moldability.

  As the heat stabilizer, a heavy metal deactivator, a phosphate ester having a pentaerythritol skeleton structure, a phosphorus compound having at least one hydroxyl group and at least one long-chain alkyl ester group, a metal carbonate, and the like are preferable. These compounds can be used alone or in combination of two or more.

  The phosphate ester having a pentaerythritol skeleton structure specifically exhibits an action of improving the melt stability of polyglycolic acid. Specific examples of the phosphate ester having a pentaerythritol skeleton structure include cyclic neopentanetetrayl bis (2,6-di-tert-butyl-4-methylphenyl) phosphite, cyclic neopentanetetrayl bis (2 , 4-di-tert-butylphenyl) phosphite, bis (monononylphenyl) pentaerythritol diphosphite, bis (4-octadecylphenyl) pentaerythritol diphosphite, and the like.

  Among the phosphorus compounds, a phosphorus compound that does not exhibit an action of inhibiting the melt stability of polyglycolic acid and has at least one hydroxyl group and at least one long-chain alkyl ester group is preferable. The number of carbon atoms in the long-chain alkyl is preferably in the range of 8-24. Specific examples of such phosphorus compounds include mono- or di-stearyl acid phosphate.

  Examples of heavy metal deactivators include 2-hydroxy-N-1H-1,2,4-triazol-3-yl-benzamide, bis [2- (2-hydroxybenzoyl) hydrazine] dodecanedioic acid, and the like. . Examples of the metal carbonate include calcium carbonate and strontium carbonate.

  The blending ratio of the heat stabilizer is usually 0.001 to 5 parts by mass, preferably 0.003 to 3 parts by mass, and more preferably 0.005 to 1 part by mass with respect to 100 parts by mass of polyglycolic acid.

  Additives include plasticizers, inorganic fillers, catalyst deactivators, heat absorbers, UV absorbers, light stabilizers, moisture-proofing agents, waterproofing agents, water repellents, lubricants, mold release agents, coupling agents, pigments, And dyes. These various additives are preferably blended in a very small amount within a range not impairing the object of the present invention. Many of these additives are usually 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 3 parts by mass or less, with respect to 100 parts by mass of polyglycolic acid, depending on the respective functions and applications. Blended.

  When the deodorant is a single layer film, the method for producing the film is not particularly limited, and various known film production methods can be used. For example, the polyglycolic acid or the polyglycolic acid and, if necessary, other thermoplastic resins, heat stabilizers, and various additives may be melt-extruded using an extruder. Further, it may be stretched after melt extrusion. Examples of the stretch molding production method include a uniaxial stretching method and a biaxial stretching method. Examples of the biaxial stretching method include a tenter method and a tube method. In particular, when a biaxially stretched film is produced, a method in which a stretching roll and a tenter stretching machine are combined is preferable. The order of the combination of roll stretching and tenter stretching is arbitrary. The order of stretching may be either the longitudinal direction (machine direction in which the sheet is fed; MD) or the transverse direction (direction crossing the machine direction; TD). The primary stretching step and the secondary stretching step may be performed continuously, but may be performed offline if desired.

  When the deodorant is a single-layer pellet, the pellet production method is not particularly limited, and various known pellet production methods can be used. For example, the above-described polyglycolic acid and necessary Depending on the situation, other thermoplastic resins, heat stabilizers, and various additives are mixed using a Henschel mixer, ribbon blender, Banbury mixer, etc., and a normal single screw extruder, twin screw extruder, Brabender or roll is used. And a method of melting and kneading at 170 to 300 ° C., preferably 190 to 250 ° C., to obtain pellets.

A manufacturing method in the case where the form of the deodorant is a package is not particularly limited, and a known method can be used.
When the deodorizer used in the present invention is a multilayer film, it is sufficient that at least one layer containing polyglycolic acid is included, and the other layers are not particularly limited.

  If necessary, the layer containing polyglycolic acid can be blended with other thermoplastic resins, heat stabilizers, and various additives. The types and ratios of these compounds to be blended are as described above. It is the same as the case of.

Examples of the other layer include a layer containing a thermoplastic resin other than polyglycolic acid or a layer containing a sealant resin.
The thermoplastic resins contained in the other layers include polyester resins, polyamide resins, polyolefin resins, ethylene-vinyl alcohol copolymer resins, polystyrene resins, polycarbonate resins, cyclic olefin resins, and polyurethane resins. Can be mentioned. Among these, polyester resins, polyamide resins, and polyolefin resins are preferable, and polyester resins are particularly preferable from the viewpoint of excellent surface characteristics such as transparency, surface hardness, printability, and heat resistance.

  Further, from the viewpoint that the stretchability, strength, etc. of the polyglycolic acid can be supplemented, a polyamide-based resin is preferable. Examples of such polyamide resins include aliphatic polyamide polymers such as nylon 6, nylon 66, nylon 11, nylon 12, nylon 69, nylon 610, and the like; nylon 6 / nylon 66, nylon 6 / nylon 69, nylon 6 / Aliphatic polyamide copolymers such as nylon 610 and nylon 6 / nylon 12. Among these, nylon 6 / nylon 66 and nylon 6 / nylon 12 are particularly preferable in terms of moldability. These aliphatic polyamide (co) polymers may be used alone or in combination of two or more.

  Further, those polyamide-based resins having a melting point of 160 to 210 ° C. are preferably used. Further, these polyamide resins include olefin resins modified with acids such as maleic acid or anhydrides thereof, ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, ionomer resins, ethylene-acetic acid. A thermoplastic resin such as a vinyl copolymer and a saponified product thereof can be contained up to about 30% by mass.

  Examples of the sealant resin contained in the other layers include those having an appropriate seal strength in the range of 90 to 250 ° C. Examples of such sealant resins include polyethylene homopolymers or copolymers, polypropylene homopolymers or copolymers, ethylene copolymers, and ionomers. These sealant resins may be used alone or in combination of two or more.

  In the case of a multilayer film, an adhesive layer can usually be interposed between the respective layers for the purpose of increasing the delamination strength. Examples of the adhesive include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenolic resins, acrylic resins, methacrylic resins, polyvinyl acetate resins, polyolefin resins such as polyethylene or polypropylene, or The resin composition which has the copolymer or modified resin, a cellulose resin, etc. as a main component of a medium can be used.

  As a configuration in the case of a multilayer film, when a layer containing polyglycolic acid is represented as “PGA”, for example, PGA / resin layer, resin layer / PGA / resin layer, PGA / resin layer / PGA / resin layer, Resin layer / PGA / resin layer / PGA / resin layer, PGA / paper, paper / PGA / paper, paper / PGA / metal foil, resin layer / PGA / paper, PGA / metal foil, resin layer / PGA / metal foil, Examples thereof include PGA / resin layer / metal foil, PGA / metal foil / resin layer, and the like.

  The layer thickness of “PGA” in the case of the multilayer film is preferably 0.1 to 50 μm, more preferably 0.5 to 30 μm, and further preferably 1 to 20 μm.

The production method of the multilayer film is not particularly limited, and a known method can be used.
The package may be a package obtained from such a film. There is no particular limitation on the method for producing a package obtained from such a multilayer film. For example, after the film is formed into a cylindrical shape by an automatic filling and packaging machine, the portion where the film is folded is heated with hot air or a seal bar. There is a method of sealing and manufacturing a seal wire of about 1 to 2 mm by sealing with one or two envelopes.

  A production method in the case where the form of the deodorant is fiber is not particularly limited, and a known method can be used. Examples thereof include a method for obtaining fibers by a melt spinning method, a dry spinning method, and a wet spinning method. The fabric can be obtained from the fibers by a known method.

When such a deodorizing agent of each form contacts a basic malodorous substance with water, this basic malodorous substance can be reduced efficiently.
Specific examples of the method for reducing the basic malodorous substance of the present invention include (I) a method for generating a basic malodorous substance and packaging the contents containing moisture in the above-described package, (II) the above-mentioned In such a package, the contents that generate basic malodorous substances are packaged, and the package contains water or water vapor. (III) The contents that generate basic malodorous substances in the above-mentioned package (IV) A method in which a polyglycolic acid or a deodorant containing polyglycolic acid as described above is contacted with water or water vapor in an atmosphere that generates a basic malodorous substance. Can be mentioned.

  Specific examples of the method (IV) include polyglycolic acid or a deodorant containing polyglycolic acid, underwear, diapers, portable toilets, pet toilets such as dogs and cats, human waste, sweat, etc. The method of reducing the basic malodorous substance generated from the metabolite containing a water | moisture content is mentioned. In addition, a method for reducing basic malodorous substances such as trimethylamine caused by initial rotting of fresh fish by using a container for storing fresh fish such as a cooler box for fishing fish containing polyglycolic acid or a deodorant containing polyglycolic acid. .

  Containers for storing fresh fish such as underwear, diapers, portable toilets, pet toilets such as dogs and cats, fishing fish cooler boxes, etc. may contain these materials mixed with polyglycolic acid in advance, After molding these, a polyglycolic acid or a deodorant containing polyglycolic acid may be separately added by a method such as impregnation.

  As another specific example, in order to reduce basic malodorous substances present in the indoor space, a highly breathable container with polyglycolic acid or a deodorant containing polyglycolic acid and water is added. You may arrange | position indoors.

(Packaging)
The package of the present invention is formed by packaging a package and a content, and placing the content generating a basic malodorous substance in a package containing at least polyglycolic acid, and performing sealed packaging. Such a package can easily reduce basic malodorous substances generated from the contents.

  As a package containing polyglycolic acid, a package obtained from a film as described above can be suitably used. The film may be a single layer film or a multilayer film. In the case of a multilayer film, it contains one or more layers containing polyglycolic acid. The method for producing the film is not particularly limited, and a known method can be used. The manufacturing method of the package obtained from the film is not particularly limited, and a known method can be used.

  The form of the package may be a form such as a bottle or cup. The bottle or cup may be a single layer bottle or a single layer cup, or may be a multilayer bottle or a multilayer cup. In the case of a multilayer bottle or multilayer cup, one or more layers containing polyglycolic acid are included. The production method of the bottle or cup is not particularly limited, and a known method can be used. The method for producing the package comprising the bottle or cup is not particularly limited, and a known method can be used.

The basic malodorous substance is as described above.
Examples of the contents include foods, diapers, garbage, used nightclothes / sheets / underwear, etc. Among them, foods are preferable.

  Examples of foods that generate basic malodorous substances generally include poultry meat, livestock meat, and seafood. In order to reduce basic malodorous substances, it is necessary to contain moisture in the package, but since the above-mentioned food normally contains moisture, it is not necessary to actively add moisture. If the contents do not contain moisture, it is necessary to add moisture to the package.

  EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these.

[Production Example 1]
In this example, a polyglycolic acid (PGA) single-layer stretched film used as a deodorant was produced as follows.

As polyglycolic acid (PGA), a homopolymer of glycolic acid was used. The polyglycolic acid (PGA) had a melt viscosity of 1,600 Pa · s measured at a temperature 20 ° C. higher than the melting point Tm (Tm + 20 ° C.) and a shear rate of 122 sec ⁻¹ . The polyglycolic acid (PGA) had a melting point (Tm) of 224 ° C., a number average molecular weight (Mn) by GPC using a hexafluoroisopropanol solvent of 55,000, and a weight average molecular weight of 104,000. It was.

  The polyglycolic acid (PGA) contains ADEKA ADEKA STAB AX-71 (monostearyl phosphate 50 mol% and distearyl phosphate 50 mol%) as a heat stabilizer in a ratio of 300 ppm, and the pellets Molded. A polyglycolic acid (PGA) single layer stretched film (thickness: 15 μm) was produced from the pellets using a stretching machine.

[Example 1]
In a 30 ml vial, one test piece of polyglycolic acid (PGA) single layer stretched film (length: 10 cm, width: 10 cm, thickness: 15 μm, weight: 0.18 g), 14 μl of 28% aqueous ammonia solution Was sealed and stored at 25 ° C. The headspace gas in the vial was sampled over time, and the concentration of ammonia (basic malodorous substance) was measured using gas chromatography. The results are shown in Table 1 and FIG.
The conditions for measuring the ammonia concentration by gas chromatography were as follows.

<Measurement conditions>
Gas chromatography: Shimadzu GC-2014 detector TCD
Column used: Chromosorb 103 60/80 3φ × 3m glass column Flow rate: 30ml / min Current: 120A
Column temperature: 80 ° C
Injection temperature: 180 ℃
Injection volume: 1ml of head space gas

[Comparative Example 1]
Without using a polyglycolic acid (PGA) monolayer stretched film, a 30 ml vial was sealed with 14 μl of 28% ammonia solution and stored at 25 ° C. As in Example 1, the headspace gas in the vial was sampled over time, and the concentration of ammonia (basic malodorous substance) was measured using gas chromatography. The measurement was blank. The results are shown in Table 1 and FIG.

[Comparative Example 2]
Except for using a polyglycolic acid (PGA) monolayer stretched film, an ethylene / vinyl alcohol copolymer (EVOH) monolayer film (Kuraray Co., Ltd .: Eval EF-CR retort film) was used. As in 1, the concentration of ammonia (basic malodorous substance) was measured. The results are shown in Table 1 and FIG.

表１の結果からポリグリコール酸（ＰＧＡ）を用いた場合（実施例１、図１ではＰＧＡ）は、ポリグリコール酸（ＰＧＡ）を用いなかった場合（比較例１、図１ではブランク）またはエチレン・ビニルアルコール共重合体を用いた場合（比較例２、図１ではＥＶＯＨ）に比べてバイアル瓶内のアンモニア（塩基性悪臭物質）の濃度を効率的に低減させる効果があることがわかった。

From the results of Table 1, when polyglycolic acid (PGA) was used (Example 1, PGA in FIG. 1), when polyglycolic acid (PGA) was not used (Comparative Example 1, blank in FIG. 1) or ethylene -It turned out that there exists an effect which reduces the density | concentration of ammonia (basic malodorous substance) in a vial bottle efficiently compared with the case where a vinyl alcohol copolymer is used (Comparative Example 2, EVOH in FIG. 1).

[Example 2]
In a 30 ml vial, one test piece of polyglycolic acid (PGA) single layer stretched film (length: 10 cm, width: 10 cm, thickness: 15 μm, weight: 0.18 g), 13 μl of 30% trimethylamine aqueous solution, Was sealed and stored at 25 ° C. The headspace gas in the vial was sampled over time, and the concentration of trimethylamine (basic malodorous substance) was measured using gas chromatography. The results are shown in Table 2 and FIG.
The conditions for measuring the trimethylamine concentration by gas chromatography were as follows.

<Measurement conditions>
Gas chromatography: Shimadzu GC-2010 detector FID
Column used: CBP10-M25-025 Capillary column Flow rate: 30 ml / min
Column temperature: 80 ° C
Injection temperature: 150 ° C
Injection volume: 0.5ml headspace gas

[Comparative Example 3]
Without using a polyglycolic acid (PGA) single-layer stretched film, only 13 μl of a 30% trimethylamine aqueous solution was sealed in a 30 ml vial and stored at 25 ° C. As in Example 2, the headspace gas in the vial was sampled over time, and the concentration of trimethylamine (basic malodorous substance) was measured using gas chromatography. The measurement was blank. The results are shown in Table 2 and FIG.

[Comparative Example 4]
Except for using a polyglycolic acid (PGA) monolayer stretched film, an ethylene / vinyl alcohol copolymer (EVOH) monolayer film (Kuraray Co., Ltd .: Eval EF-CR retort film) was used. As in 2, the concentration of trimethylamine (basic malodorous substance) was measured. The results are shown in Table 2 and FIG.

〔実施例３〕
保存温度を２５℃から３７℃に換えた以外は、実施例２と同様にしてトリメチルアミン（塩基性悪臭物質）の濃度を測定した。結果を表３および図３に示す。

Example 3
The concentration of trimethylamine (basic malodorous substance) was measured in the same manner as in Example 2 except that the storage temperature was changed from 25 ° C to 37 ° C. The results are shown in Table 3 and FIG.

[Comparative Example 5]
The concentration of trimethylamine (basic malodorous substance) was measured in the same manner as in Comparative Example 3 except that the storage temperature was changed from 25 ° C to 37 ° C. The results are shown in Table 3 and FIG.

[Comparative Example 6]
The concentration of trimethylamine (basic malodorous substance) was measured in the same manner as in Comparative Example 4 except that the storage temperature was changed from 25 ° C to 37 ° C. The results are shown in Table 3 and FIG.

表２および表３の結果からポリグリコール酸（ＰＧＡ）を用いた場合（実施例２および実施例３、図２および図３ではＰＧＡ）は、ポリグリコール酸（ＰＧＡ）を用いなかった場合（比較例３および比較例５、図２および図３ではブランク）またはエチレン・ビニルアルコール共重合体を用いた場合（比較例４および６、図２および図３ではＥＶＯＨ）に比べてバイアル瓶内のトリメチルアミン（塩基性悪臭物質）の濃度を効率的に低減させる効果があることがわかった。また、保存温度を２５℃から３７℃に上げると、トリメチルアミン（塩基性悪臭物質）の濃度の低減速度が速くなることがわかった。

From the results of Table 2 and Table 3, when polyglycolic acid (PGA) was used (Example 2 and Example 3, PGA in FIGS. 2 and 3), when polyglycolic acid (PGA) was not used (comparison) Trimethylamine in the vial compared to Example 3 and Comparative Example 5, blank in FIGS. 2 and 3) or using ethylene-vinyl alcohol copolymer (Comparative Examples 4 and 6, EVOH in FIGS. 2 and 3) It was found that there was an effect of efficiently reducing the concentration of (basic malodorous substance). It was also found that when the storage temperature was raised from 25 ° C. to 37 ° C., the concentration reduction rate of trimethylamine (basic malodorous substance) increased.

Example 4
In a 30 ml vial, one test piece of polyglycolic acid (PGA) single layer stretched film (length: 10 cm, width: 10 cm, thickness: 15 μm, weight: 0.18 g), 0.5 ml of distilled water, Then, 8 μl of triethylamine was added and sealed, and stored at 37 ° C. (humidified conditions). The headspace gas in the vial was sampled over time, and the concentration of triethylamine (basic malodorous substance) was measured using gas chromatography. The results are shown in Table 4 and FIG.
The conditions for measuring the triethylamine concentration by gas chromatography were as follows.

<Measurement conditions>
Gas chromatography: Shimadzu GC-2014 detector FID
Column used: PEG-20M 20% + Chromosoeb WAW 80/100 3φ × 3m glass column Flow rate: 30 ml / min
Column temperature: 80 ° C
Injection temperature: 150 ° C
Injection volume: 0.5ml headspace gas

[Comparative Example 7]
Without using a polyglycolic acid (PGA) single-layer stretched film, 0.5 ml of distilled water and 8 μl of triethylamine were sealed in a 30 ml vial and stored at 37 ° C. (humidified conditions). As in Example 4, the headspace gas in the vial was sampled over time, and the concentration of triethylamine (basic malodorous substance) was measured using gas chromatography. The measurement was blank. The results are shown in Table 4 and FIG.

[Comparative Example 8]
Except for using a polyglycolic acid (PGA) monolayer stretched film, an ethylene / vinyl alcohol copolymer (EVOH) monolayer film (Kuraray Co., Ltd .: Eval EF-CR retort film) was used. As in 4, the concentration of triethylamine (basic malodorous substance) was measured. The results are shown in Table 4 and FIG.

表４の結果から、ポリグリコール酸（ＰＧＡ）を用いた場合（実施例４、図４ではＰＧＡ）は、ポリグリコール酸（ＰＧＡ）を用いなかった場合（比較例７、図４ではブランク）またはエチレン・ビニルアルコール共重合体を用いた場合（比較例８、図４ではＥＶＯＨ）に比べてバイアル瓶内のトリエチルアミン（塩基性悪臭物質）の濃度を効率的に低減させる効果があることがわかった。

From the results of Table 4, when polyglycolic acid (PGA) was used (Example 4, PGA in FIG. 4), when polyglycolic acid (PGA) was not used (Comparative Example 7, blank in FIG. 4) or It was found that there was an effect of efficiently reducing the concentration of triethylamine (basic malodorous substance) in the vial as compared with the case of using the ethylene / vinyl alcohol copolymer (EVOH in Comparative Example 8 and FIG. 4). .

[Comparative Example 9]
In a 30 ml vial, put one test piece of polyglycolic acid (PGA) single layer stretched film (length: 10 cm, width: 10 cm, thickness: 15 μm, weight: 0.18 g) and 4 μl of triethylamine. Sealed and stored at 37 ° C. (dry conditions). The headspace gas in the vial was sampled over time, and the concentration of triethylamine (basic malodorous substance) was measured using gas chromatography. The results are shown in Table 5 and FIG.
The conditions for measuring the triethylamine concentration by gas chromatography were as follows.

<Measurement conditions>
Gas chromatography: Shimadzu GC-2014 detector FID
Column used: PEG-20M 20% + Chromosoeb WAW 80/100 3φ × 3m glass column Flow rate: 30 ml / min
Column temperature: 80 ° C
Injection temperature: 150 ° C
Injection volume: 0.5ml headspace gas

[Comparative Example 10]
Without using a polyglycolic acid (PGA) monolayer stretched film, 4 μl of triethylamine was sealed in a 30 ml vial and stored at 37 ° C. (dry conditions). As in Comparative Example 9, the headspace gas in the vial was sampled over time, and the concentration of triethylamine (basic malodorous substance) was measured using gas chromatography. The measurement was blank. The results are shown in Table 5 and FIG.

[Comparative Example 11]
A comparative example except that instead of a polyglycolic acid (PGA) single layer stretched film, an ethylene / vinyl alcohol copolymer (EVOH) single layer film (Kuraray Co., Ltd .: Eval EF-CR film for retort) was used. As in 9, the concentration of triethylamine (basic malodorous substance) was measured. The results are shown in Table 5 and FIG.

表４および表５の結果から、加湿条件とドライ条件とを比較すると、ドライ条件ではポリグリコール酸（ＰＧＡ）を用いた場合（比較例９、図５ではＰＧＡ）、ポリグリコール酸（ＰＧＡ）を用いなかった場合（比較例１０、図５ではブランク）、エチレン・ビニルアルコール共重合体を用いた場合（比較例１１、図５ではＥＶＯＨ）、いずれの場合も差異がなく、ポリグリコール酸（ＰＧＡ）を用いた場合によるトリエチルアミン（塩基性悪臭物質）の低減効果は認められなかった。しかし、加湿条件ではポリグリコール酸（ＰＧＡ）を用いた場合、速やかにトリエチルアミン（塩基性悪臭物質）の濃度を低減させた。このことより、ポリグリコール酸（ＰＧＡ）を用いる塩基性悪臭物質の低減には水の存在が不可欠であることがわかった。

From the results of Table 4 and Table 5, when the humidification condition and the dry condition are compared, the polyglycolic acid (PGA) is used in the dry condition (Comparative Example 9, PGA in FIG. 5). When not used (Comparative Example 10, blank in FIG. 5), when ethylene / vinyl alcohol copolymer was used (Comparative Example 11, EVOH in FIG. 5), there was no difference in either case, and polyglycolic acid (PGA ) Was not observed to reduce triethylamine (basic malodorous substance). However, when polyglycolic acid (PGA) was used under humidifying conditions, the concentration of triethylamine (basic malodorous substance) was quickly reduced. This indicates that the presence of water is indispensable for reducing basic malodorous substances using polyglycolic acid (PGA).

Example 5
Package A was manufactured as follows, and the reduction effect of ammonia (basic malodorous substance) was evaluated.

As polyglycolic acid (PGA), a homopolymer of glycolic acid was used. The polyglycolic acid (PGA) had a melt viscosity of 1150 Pa · s measured at 270 ° C. and a shear rate of 122 sec ⁻¹ . The polyglycolic acid (PGA) had a melting point Tm of 250 ° C., a number average molecular weight of 110,000 by GPC using a hexafluoroisopropanol solvent, and a weight average molecular weight of 240,000.

  Pellet (hereinafter also referred to as “PGA”) formed from the polyglycolic acid (PGA), Belpet IFG-8L (hereinafter also referred to as “PET”) manufactured by Belboriducts, Inc., and Amilan manufactured by Toray Industries, Inc. From CM6241FS (hereinafter also referred to as “Ny6-66”) and Idemitsu Petrochemical's MORETECH 0238CN (hereinafter also referred to as “LLDPE”), multilayer film A (hereinafter referred to as “VS-20 (PGA configuration)” having the following configuration. ) "). In addition, as an adhesive between each layer, Modic F563 manufactured by Mitsubishi Chemical Corporation was used.

(Configuration of multilayer film A)
VS-20 (PGA configuration): PET // Ny6-66 // PGA // LLDPE
Using the multilayer film A, a package A having a three-side seal with an inner dimension of 11 cm × 11 cm was produced. However, the PET side of the multilayer film A was the outside of the package A.

  As the contents to be included in the package A, 6 cm × 6 cm gauze impregnated with 100 μl of 28% ammonia water was used. A plastic tray (9 cmφ round tray) on which the gauze was placed was placed in the package A and sealed and packaged to obtain a package A (inner bag).

  Next, an Al pouch having the following configuration was fabricated from aluminum (hereinafter also referred to as “Al”), PET, and (unstretched polypropylene) (hereinafter also referred to as “CPP”). As an adhesive between the layers, Takelac A-620 manufactured by Mitsui Chemicals Polyurethane Co., Ltd. was used. As a curing agent, Takenate A-65 manufactured by Mitsui Chemicals Polyurethane Co., Ltd. was used.

(Configuration of Al pouch)
Al pouch: PET // Al // CPP
Using the Al pouch, a package D (outer bag) having a three-side seal with an inner size of 12 cm × 12 cm was produced. However, the PET side of the Al pouch was the outside of the package D. The package A (inner bag) was included in the package D (outer bag) (see FIG. 6). Let stand at room temperature (25 ° C.) for 4 days to determine the ammonia concentration in the package A (inner bag) and the ammonia concentration outside the package A (inner bag) and in the package D (outer bag). Measured by gas chromatography. The amount of residual ammonia was calculated from these ammonia concentrations. The results are shown in Table 6.

In addition, the calculation method of ammonia residual amount is as follows.
First, 2.8 μL and 28 μL of 28% aqueous ammonia were placed in a 30 ml vial and heated in a high-temperature bath at 130 ° C. for 3 minutes. After heating, the headspace gas in the vial was sampled and the ammonia concentration was measured using gas chromatography. A calibration curve was created using this result, and the residual ammonia amount was calculated from the result.

[Comparative Example 12]
The effect of reducing ammonia (basic malodorous substance) was evaluated in the same manner as in Example 5 except that the package A was changed to the package B shown below. The results are shown in Table 6.

The package B was manufactured as follows.
A multi-layer film B (hereinafter referred to as “VS-20 (EVOH configuration)” having the following configuration from Sojanol H4815 (hereinafter also referred to as “EVOH”) manufactured by Nippon Gosei Co., Ltd., PET, Ny6-66, and LLDPE. ) "). As an adhesive between the layers, Modic F563 manufactured by Mitsubishi Chemical Corporation was used.

(Configuration of multilayer film B)
VS-20 (EVOH configuration): PET // Ny6-66 // EVOH // LLDPE
Using the multilayer film B, a package B having a three-sided seal with an inner dimension of 11 cm × 11 cm was produced. However, the PET side in the multilayer film B was the outside of the package B.

  As the contents to be included in the package B, a 6 cm × 6 cm gauze impregnated with 100 μl of 28% ammonia water was used. A plastic tray (9 cmφ round tray) on which the gauze was placed was placed in the package B and hermetically packaged to obtain a package B (inner bag).

[Comparative Example 13]
The effect of reducing ammonia (basic malodorous substance) was evaluated in the same manner as in Example 5 except that the package A was changed to the package C shown below. The results are shown in Table 6.

The package C was manufactured as follows.
A multilayer film C (hereinafter also referred to as “Al pouch”) having the following structure is formed from aluminum (hereinafter also referred to as “Al”), PET, and unstretched polypropylene (hereinafter also referred to as “CPP”). Produced. As an adhesive between the layers, Takelac A-620 manufactured by Mitsui Chemicals Polyurethane Co., Ltd. was used. As a curing agent, Takenate A-65 manufactured by Mitsui Chemicals Polyurethane Co., Ltd. was used.

(Configuration of multilayer film C)
Al pouch: PET // Al // CPP
Using the multilayer film C, a package C having a three-side seal with an inner dimension of 11 cm × 11 cm was produced. However, the PET side of the multilayer film C was the outside of the package C.

  As the contents to be included in the package C, 6 cm × 6 cm gauze impregnated with 100 μl of 28% ammonia water was used. A plastic tray (9 cmφ round tray) on which the gauze was placed was placed in the packaging body C and hermetically packaged to obtain a package C (inner bag).

表６の結果から、ＶＳ−２０（ＥＶＯＨ構成）の場合では、包装物Ｂの内外でアンモニアが検出されたが、ＶＳ−２０（ＰＧＡ構成）の場合では、包装物Ａの内外ともアンモニアが検出されなかったことがわかった。

From the results in Table 6, in the case of VS-20 (EVOH configuration), ammonia was detected inside and outside of package B, but in the case of VS-20 (PGA configuration), ammonia was detected both inside and outside of package A. I knew it wasn't done.

  In addition, ammonia was detected only inside the package C using the Al pouch, and no ammonia was detected outside, so it is considered that there was no ammonia leak from the outer bag using the Al pouch. . Therefore, in the case of VS-20 (PGA configuration), it is appropriate to consider that the residual ammonia amount is reduced by the multilayer film A.

In the case of VS-20 (EVOH configuration), since ammonia was detected both inside and outside the package B, it is considered that the multilayer film B did not have an effect of reducing the residual amount of ammonia.
In the case of VS-20 (PGA configuration), the residual amount of ammonia is reduced by the polyglycolic acid (PGA) layer of the multilayer film A, and the ammonia (basic malodorous substance) reducing effect of the polyglycolic acid (PGA) is exhibited. It is thought.

Example 6
In a 30 ml vial, one test piece of polyglycolic acid (PGA) single layer stretched film (length: 10 cm, width: 10 cm, thickness: 15 μm, weight: 0.18 g), 14 μl of 28% aqueous ammonia solution Was sealed and stored at 25 ° C. The headspace gas in the vial was sampled over time, and the concentration of ammonia (basic malodorous substance) was measured using gas chromatography. The results are shown in FIG. Further, the residual ammonia amount was calculated in the same manner as in Example 5. The results are shown in Table 7.
The conditions for measuring the ammonia concentration by gas chromatography were as follows.

<Measurement conditions>
Gas chromatography: Shimadzu GC-2014 detector TCD
Column used: Chromosorb 103 60/80 3φ × 3m glass column Flow rate: 30ml / min Current: 120A
Column temperature: 80 ° C
Injection temperature: 180 ℃
Injection volume: 1ml of head space gas

Example 7
Except that the polyglycolic acid (PGA) single layer stretched film was changed to a polyglycolic acid (PGA) single layer stretched film to which carbodiimide (hereinafter also referred to as “CDI”) was added, the same procedure as in Example 6 was followed. The reduction effect of (basic malodorous substance) was evaluated. The results are shown in Table 7 and FIG.

この結果からＣＤＩを添加しないポリグリコール酸（ＰＧＡ）単層延伸フィルムの方がより速やかにアンモニア濃度を低減する効果を発揮したが、ＣＤＩを添加したポリグリコール酸（ＰＧＡ）単層延伸フィルムでもアンモニア濃度を低減する効果を有することがわかった。このことより、どちらの場合でも効果を有するが、アンモニア濃度を低減する速度に若干の差が出ることがわかった。

From this result, the polyglycolic acid (PGA) single-layer stretched film without addition of CDI exhibited the effect of reducing the ammonia concentration more rapidly, but the polyglycolic acid (PGA) single-layer stretched film with addition of CDI also exhibited ammonia. It was found to have an effect of reducing the concentration. From this, it was found that in both cases, the effect is obtained, but there is a slight difference in the rate of reducing the ammonia concentration.

  The film added with CDI to suppress hydrolyzability has a slower rate of reducing the ammonia concentration than the film without added CDI. It was suggested that the presence of degradation products produced by hydrolysis of the film is greatly involved.

[Confirmation of molecular weight change of polyglycolic acid (PGA)]
[Confirmation experiment 1]
The following pretreatment was performed on the polyglycolic acid (PGA) single layer stretched film, and the molecular weight by GPC was measured. The results are shown in Table 8.

(Preprocessing)
To 5 mg of sample, 200 μl of dimethyl sulfoxide was added and allowed to act in an oil bath at 160 ° C. for 2 minutes to dissolve the sample. Next, it was cooled in running water, 5 ml of HFIP (hexafluoroisopropanol) was added and dissolved, and the sample solution was filtered.

[Confirmation experiment 2]
A 30 ml vial was filled with a polyglycolic acid (PGA) monolayer stretched film and 14 μl of 28% aqueous ammonia solution, and stored at 25 ° C. After storage for 1 hour, the polyglycolic acid (PGA) monolayer stretched film was subjected to the same pretreatment as in Confirmation Experiment 1, and the molecular weight was measured by GPC. The results are shown in Table 8.

[Verification Experiment 3]
A 30 ml vial was filled with a polyglycolic acid (PGA) monolayer stretched film and 13 μl of a 30% aqueous trimethylamine solution, and stored at 37 ° C. After storage for 3 days, the polyglycolic acid (PGA) monolayer stretched film was subjected to the same pretreatment as in Confirmation Experiment 1, and the molecular weight was measured by GPC. The results are shown in Table 8.

[Verification Experiment 4]
A 30 ml vial was charged with a polyglycolic acid (PGA) monolayer stretched film and 4 μl of triethylamine, 0.5 ml of water was added, sealed and stored at 37 ° C. After storage for 3 days, an appropriate pretreatment was performed on the polyglycolic acid (PGA) single layer stretched film, and the molecular weight by GPC was measured. The results are shown in Table 8.

表８の結果から、ポリグリコール酸（ＰＧＡ）は、アンモニア、トリメチルアミン、トリエチルアミンなどの塩基性悪臭物質および水の存在下で保存すると、分子量が低下することがわかった。すなわち、ポリグリコール酸（ＰＧＡ）の分解が起こったと考えられる。特にアンモニアと水との存在下では、Ｍｗ／Ｍｎの値が大きくなっていることから、ポリグリコール酸（ＰＧＡ）の分解が進み、低分子量の物質の割合が大きくなったと考えられる。

From the results of Table 8, it was found that polyglycolic acid (PGA) has a molecular weight that is reduced when stored in the presence of basic malodorous substances such as ammonia, trimethylamine, and triethylamine, and water. That is, it is considered that polyglycolic acid (PGA) was decomposed. In particular, in the presence of ammonia and water, the value of Mw / Mn is large, so it is considered that the decomposition of polyglycolic acid (PGA) has progressed and the proportion of low molecular weight substances has increased.

1: Inner bag (package A in the case of Example 5, package B in the case of Comparative Example 12, package C in the case of Comparative Example 13)
2: Outer bag (Al pouch)
3: Ammonia impregnated gauze 4: Round tray

Claims (3)

  A method for reducing a basic malodorous substance, comprising contacting polyglycolic acid, water, and a basic malodorous substance.   A method for reducing a basic malodorous substance, which comprises contacting a deodorant containing polyglycolic acid as a deodorizing component, water, and a basic malodorous substance.   The method of reducing a basic malodorous substance according to claim 2, wherein the deodorant is in the form of a film, pellet, package, powder, fiber, or fabric.

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