JP2017035196A - Deodorant sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deodorant sheet having a long-lasting deodorant effect that deodorizes not only sulfur-based malodorous substances such as hydrogen sulfide and methyl mercaptan, but also malodorous substances such as lower fatty acids and body odor components.SOLUTION: A deodorant sheet is made of paper carrying a glassy deodorant composed of (alkali)-(alkaline earth)-(borosilicate) glass containing a copper component or (alkali)-(alkaline earth)-(silicate) glass containing a copper component. The copper component contained in the glass catalyzes decomposition of malodorous components. The deodorant sheet is suitable to be used for a food bag, a confectionery bag, a shopping bag, a garbage bag, a diaper bag, or the like.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a deodorizing paper carrying a glassy deodorant.

As a technique for imparting a specific function to paper, for example, soluble glass that dissolves B ₂ O ₅ effective for mite control is mixed as a fine powder with a binder and sprayed on the surface of the paper to provide an insect repellent function. A method to obtain a crumpled paper (Patent Document 1) and a soluble glass that elutes silver ions having functions such as deodorization and antibacterial as a fine powder mixed with a binder and water to make a slurry, and a paper sheet is immersed therein In addition, a method (Patent Document 2) is disclosed in which paper having functions such as deodorization and antibacterial is obtained through the steps of impregnation and drying.

  However, since the techniques of Patent Documents 1 and 2 exhibit a specific function by the components eluted from the soluble glass, the elution progresses and the specific function (for example, Patent Document 1 has an antifungal effect). In Patent Document 2, it is inevitable that the deodorizing effect and the antibacterial effect are reduced, and there is a problem that it is not suitable for application to a product that is expected to be used for a long period of time.

  Further, regarding Patent Document 2, silver ions have an antibacterial effect, and thus have an effect of preventing malodors produced by bacteria. However, there is no deodorizing effect on malodorous substances such as lower fatty acids and body odor components, and these odors are mainly used. There is a problem that it is not suitable for application to products used in the nursing field.

JP-A-5-246812 JP-A-7-202227

  Therefore, the object of the present invention is to solve the above-mentioned conventional problems, have excellent deodorizing effect, and not only sulfur-based malodorous substances such as hydrogen sulfide and methyl mercaptan, but also malodorous substances such as lower fatty acids and body odor components. Another object is to provide a deodorizing paper having a function of deodorizing.

  The present invention made to solve the above problems is a deodorizing paper in which a glassy deodorant is supported between fibers constituting the paper or on the surface of the paper, and this glassy deodorant is a copper component. Of alkali-alkaline earth-borosilicate glass containing copper or alkali-alkaline earth-silicate glass containing copper component, and the function of decomposing malodorous components by the catalytic action of the copper component held in the glass It is characterized by having. Here, “paper” refers to paper made by interlacing and attaching plant fibers and other fibers, as well as synthetic paper, synthetic fiber paper, synthetic pulp paper, and waste paper pulp made using synthetic polymer substances. Paper and paper mixed with fibrous inorganic materials are also included.

In addition, as described in claim 2, it is preferable that the content of the vitreous deodorant supported between the fibers constituting the paper is 0.1 to 10% by mass. Moreover, as described in claim 3, it is preferable that the content of the vitreous deodorant carried on the paper surface is 0.1 to 5 g / m ² . Further, as described in claim 4, the vitreous deodorant is preferably a powder having a D _{96 of} 40 μm or less. Further, as described in claim 5, the above-mentioned deodorant paper can be laminated, or can be laminated with paper not containing a glassy deodorant to obtain a laminated paper having a laminated structure.

  The deodorizing paper of the present invention holds a glassy deodorant composed of an alkali-alkaline earth-borosilicate glass containing a copper component or an alkali-alkaline earth-silicate glass containing a copper component on the paper. The malodorous component is decomposed by the catalytic action of the copper component held in the glass.

  Various deodorizers using soluble glass have been developed, but they all adsorb malodorous components chemically or physically to specific components eluted from the soluble glass. A “glass agent exhibiting a deodorizing effect by catalytic action” has not been known. As a result of many years of research, the present inventors have found that "the copper component contained in the glass having the above composition functions as a catalyst, promotes the decomposition reaction of the sulfur-based malodorous substance, and deodorizes the sulfur-based malodorous substance. We found a new finding that

In the present invention, as described above, since it has a mechanism for promoting the decomposition reaction of the sulfur-based malodorous substance using the copper component contained in the glass as a catalyst, compared to the conventional technology using chemical adsorption and physical adsorption, The deodorizing capacity can be increased, and the deodorizing effect can be exhibited stably over a long period of time. That is, both conventional chemical adsorption and physical adsorption depend on the surface exposure amount of the adsorbent, and the deodorization limit is determined by the exposure amount. However, in the present invention, since the catalytic reaction is used, the exposure amount is small. Even so, a large total deodorizing amount can be obtained. For this reason, if attention is paid only to the deodorizing amount, a small amount of the glassy deodorant may be added, but in order to add a deodorizing speed, as described above, the glassy material supported between the fibers constituting the paper. The content of the deodorant is preferably 0.1 to 10% by mass, and the content of the glassy deodorant supported on the paper surface is preferably 0.1 to 5 g / m ² .

  The vitreous deodorant used in the present invention can exhibit an excellent deodorizing effect particularly with respect to methyl mercaptan. That is, this glassy deodorant catalytically oxidatively decomposes methyl mercaptan to produce dimeric dimethyl disulfide. At this time, radicals are generated and oxidatively decomposed. Similarly, similar oxidative decomposition is possible for other gases. However, the odor that can be deodorized is not limited to sulfur-based odor substances. Specific examples include lower fatty acids, acetic acid known as body odor (sweat, foot odor), isovaleric acid, propionic acid, normal butyric acid, normal valeric acid, and caproic acid, a medium chain fatty acid, as defined by the Malodor Control Law. Also, enanthic acid and trans-2-nonenal, known as an aging odor, can be deodorized. In general, those having 2 to 4 carbon atoms are referred to as short chain fatty acids (lower fatty acids), but in this specification, acetic acid having 1 carbon atom and 5 valeric acids are also treated as lower fatty acids.

  The deodorizing paper of the present invention is suitable for applications where a deodorizing effect is desired, such as food packaging, garbage, plastic bags, diapers, and the like. The main components of a diaper odor are hydrogen sulfide, methyl mercaptan, and lower fatty acids, and the deodorizing effect of lower fatty acids is required in the nursing field. The main component of the garbage odor is also hydrogen sulfide, methyl mercaptan, and propionic acid, which is one of lower fatty acids, and the deodorized paper of the present invention is suitable for these uses. Furthermore, there is a case where garbage is hard to burn in garbage incineration facilities such as local governments because of the recent separation of garbage. Since the vitreous deodorant of the present invention promotes oxidative decomposition by radicals, it has not only a deodorizing effect but also a function as a combustion promoting catalyst. That is, it is suitable for use on paper classified as combustible waste.

  In addition, removal of malodorous components may be required in the technical fields of pharmaceuticals, electronic parts and precision equipment. That is, hydrogen sulfide and acetic acid may be generated by outgas from chemicals used in the manufacturing process, and these are not only bad odors but also corrosive gases that lead to metal corrosion and product deterioration. By using the deodorizing paper of the present invention, it can contribute to the extension of product life and stabilization of product quality. As described above, the deodorant paper (deodorant multilayer paper) of the present invention is a medical wrapping paper, a food wrapping paper, a freshness preserving paper, a paper apparel, a wallpaper, a tissue paper, a toilet paper, a separate sheet, a cardboard, etc. It can be used for various applications.

It is typical sectional drawing which shows the deodorizing paper of 1st Embodiment. It is typical sectional drawing which shows the deodorizing paper of 2nd Embodiment. 10 is a graph showing the results of Example C.

Embodiments of the present invention will be described below.
As shown in FIG. 1, the deodorizing paper of the first embodiment is obtained by containing a glassy deodorant 2 powder between the fibers 1 constituting the paper, and the deodorizing paper of the second embodiment. The odor paper is obtained by forming a deodorizing layer 3 containing a glassy deodorant on the surface of the paper. The vitreous deodorant is composed of an alkali-alkaline earth-borosilicate glass containing a copper component or an alkali-alkaline earth-silicate glass containing a copper component, and is a powder having a D _{96 of} 40 μm or less. It is desirable.

Here, D ₉₆ means a particle size at which the integral value when the particle size distribution measurement is performed and the cumulative distribution is 96%. Or vitreous deodorant 2 becomes liable to fall off from the paper when D ₉₆ is more than 40 [mu] m, smoothness is deteriorated. When the particle size is less than 1 μm, the efficiency of pulverizing and classifying glass is extremely lowered, which is not preferable in production. A particle size of about 1 to 25 μm is practical. Such a vitreous deodorant can be produced by a method in which the raw material for preparation is melted and rapidly cooled to obtain a pre-molded product, and then pulverized. For the pulverization, a generally known pulverizer (for example, a ball mill, a bead mill, a jet mill, a CF mill, etc.) can be used, and it may be dry or wet. The composition of the glassy deodorant will be described below.

(Alkali-alkaline earth-borosilicate glass)
The alkali-alkaline earth-borosilicate glass containing the above-described copper component is SiO ₂ : 46 to 70 mol%, B ₂ O ₃ + R ₂ O (R: alkali metal): 15 to 50 mol%, R′O. (R ′: alkaline earth metal): 0 to 10 mol%, Al ₂ O ₃ : 0 to 6%, CuO: 0.01 to 23 mol%. _Here, B ₂ O 3: _{5~20 mol%,} R 2 O: can be 10 to 30 mol%.

A preferred composition of the vitreous _deodorants, SiO 2: 51 to 63 _{mol%, B 2 O 3 + R} 2 O: 21~39 mol%, R'O: 2 to 7 _mol%, Al _{2 O} 3: 0 -5.5%, CuO: 1-13 mol%. _Here, B ₂ O 3: _{8~17 mol%,} R 2 O: can be 13 to 22 mol%.

The most preferred composition of this vitreous _deodorants, SiO 2: 53-62 _{mol%, B} 2 O 3: _{10~17 mol%,} R 2 O: _13~19 mol%, R'O: 3 to 6 _{mol%, Al 2 O 3: 0~4.5} %, CuO: 4~13 are mole%. Below, each glass composition is demonstrated in detail.

(SiO ₂ )
SiO ₂ is a main component that forms the structural skeleton of glass, and its content is 46 to 70 mol%, preferably 51 to 63 mol%, and more preferably 53 to 62 mol%. If it is less than 46 mol%, the chemical durability of the glass becomes insufficient, and the glass tends to devitrify, which is not preferable. Furthermore, if it is less than 46 mol%, the water resistance of the glass becomes insufficient, and copper ions are more likely to elute in the presence of moisture (including moisture in the atmosphere). Since the deodorizing effect by the sulfurization reaction which occurs by this becomes strong, it is not preferable. If it exceeds 70 mol%, the melting point increases, which makes glass melting difficult and also causes an increase in viscosity.

(B ₂ O ₃ )
B ₂ O ₃ is a component that improves the solubility and clarity of the glass, and in a specific composition, it also becomes a component that forms the structural skeleton of the glass. B ₂ O ₃ greatly affects the stability of the glass depending on its content, and in the present invention, the meaning as a flux of glass is large. Its _content, in consideration of the volatilization amount of B 2 _{O 3,} 5 to 20 mol%, preferably 8 to 17 mol%, further preferably 10 to 17 mol%. When it exceeds 20 mol%, B ₂ O ₃ is not preferred because it tends to volatilize in the melting process and the composition control becomes difficult.

(R ₂ O)
R ₂ O (R = Li, Na, K) breaks the bond between Si and O in the glass structure skeleton to form non-crosslinked oxygen, resulting in a decrease in glass viscosity, moldability and solubility. And a flux similar to B ₂ O ₃ . The content of one or more of R ₂ O is 10 to 30 mol% in total, preferably 13 to 22 mol%, more preferably 13 to 19 mol%, considering the content ratio with multiple components. And When it exceeds 30 mol%, the chemical durability of the glass becomes insufficient. Specifically, a whitening phenomenon called bloom is caused by a reaction between the glass agent and moisture in the atmosphere. The occurrence of bloom is undesirable because it reduces the contact area with malodorous gas.

(B ₂ O ₃ + R ₂ O)
As mentioned above, both B ₂ O ₃ and R ₂ O are used as fluxing agents. The range in which the total content of B ₂ O ₃ and R ₂ O is 15 to 50 mol%, preferably 21 to 39 mol%, is a region that safely exhibits the deodorizing effect. If it is less than 15 mol%, the meltability of the glass becomes insufficient, and devitrification tends to occur during molding, which is not preferable. If it exceeds 50 mol%, the water resistance of the glass becomes insufficient, and copper ions are likely to elute in the presence of moisture (including moisture in the atmosphere), resulting in ion elution rather than deodorizing effect due to catalysis. Since the deodorizing effect by a sulfurization reaction becomes strong, it is not preferable. On the other hand, if it exceeds 50 mol%, phase separation is likely to occur during melting, and the deodorizing effect of the glass agent becomes insufficient accordingly.

(R'O)
R′O (R ′ = Mg, Ca, Sr, Ba) is a component that improves the chemical durability of the glass. The content is one or two or more of R′O (R ′ = Mg, Ca, Sr, Ba) in a total of 0 to 10 mol%, preferably 2 to 7 mol%, more preferably 3 to 6 mol. %. If it exceeds 10 mol%, the viscosity at the time of melting becomes high and the glass tends to be devitrified, which is not preferable. Note that R′O is not an essential component in the deodorant of the invention, and its content may be 0 mol%, but is preferably 2 mol% or more.

(Al ₂ O ₃ )
Al ₂ O ₃ is a component that improves the chemical durability of the glass and affects the crystal structure stability. Further, Al ₂ O ₃ functions to suppress the phase separation of the glass and increase the homogeneity of the glass agent. Since the viscosity and the addition may affect the redox state of copper ions in the glass, its content is 6 mol% or less, preferably 5.5 mol% or less, most preferably 4 .5 mol% or less.

(CuO)
CuO functions as a catalyst, accelerates the decomposition reaction of the sulfurous malodorous substance, and exhibits the deodorizing effect of the sulfurous malodorous substance. The content is 0.01 to 23 mol%, preferably 1 to 13 mol%, more preferably 4 to 13 mol%. If it exceeds 23 mol%, undissolved material tends to remain, and metal copper tends to precipitate during rapid cooling or processing, which is not preferable. Since the glass is discolored with the deposition of metallic copper, it is not suitable for applications where discoloration of the glass is a problem. Moreover, when it precipitates as metallic copper, poisoning will advance. On the other hand, if CuO is included as a glass component, poisoning does not proceed easily, and the catalytic function can be stably exhibited over a long period of time.

(Other trace components)
In addition to the above components, ZnO, SrO, BaO, TiO ₂ , ZrO ₂ , Nb ₂ O ₅ , P ₂ O ₅ , Cs ₂ O, Rb ₂ O, TeO ₂ , BeO, GeO ₂ , Bi ₂ can be used as trace components. O ₃ , La ₂ O ₃ , Y ₂ O ₃ , WO ₃ , MoO ₃ , Fe ₂ O ₃ or the like can also be included. Furthermore, F, Cl, SO ₃ , Sb ₂ O ₃ , SnO ₂ , Ce, or the like may be added as a clarifier.

(Alkali-alkaline earth-silicate glass)
In the present invention, an alkali-alkaline earth-silicate glass containing a copper component can also be used as the vitreous deodorant. This _glass, SiO 2: 50-70 _mol%, R 2 O: _10~33 mol%, R'O: 0 to 15 _{mol%, Al 2 O 3: 0~6} %, CuO: 0.01~23 It is a glass containing mol%.

A preferred composition of the vitreous _deodorants, SiO 2: 55 to 70 _mol%, R 2 O: _12~24 mol%, R'O: 2 to 10 _{mol%, Al} 2 O 3: _0~5.5 %, CuO: 1 to 20 mol%. The most preferred composition of this vitreous _deodorants, SiO 2: 55 to 65 _mol%, R 2 O: _12~20 mol%, R'O: 3 to 7 _{mol%, Al} 2 O 3: _0~5 %, CuO: 4 to 13 mol%.

Unlike the alkali-alkaline earth-borosilicate glass described above, the alkali-alkaline earth-silicate glass does not contain B ₂ O ₃ , so the numerical range of the composition is slightly changed. Is the same as alkali-alkaline earth-borosilicate glass.

  The glassy deodorant comprising the alkali-alkaline earth-borosilicate glass containing the copper component or the alkali-alkaline earth-silicate glass containing the copper component is used between the fibers constituting the paper or the paper. Contained on the surface. The type of paper is preferably cellulose fiber, but is not particularly limited. Wood pulp, non-wood pulp (wood, sugar cane, reed, kenaf, mulberry, mulberry, mitsumata, bamboo ), Synthetic pulp (polypropylene, polyethylene, polyethylene terephthalate, polyvinyl chloride, polystyrene, alumina fiber, carbon fiber, glass fiber, zirconia fiber, alumina / silica fiber, etc.), recycled pulp That's fine. For example, any paper such as Japanese paper, western paper, neutral paper, recycled paper, and synthetic paper can be used.

As described above, when it is carried between the fibers constituting the paper, the content of the glassy deodorant in the deodorant paper is 0.1 to 10% by mass, and when it is carried on the surface of the paper. The glassy deodorant content is preferably 0.1 to 5 g / m ² . This is because if it is less than this range, the deodorizing effect is insufficient, while if it exceeds this range, the characteristics of the paper, that is, flexibility and smoothness may be lost. In the present invention, since the vitreous deodorant exhibits a deodorizing function due to a catalytic effect, the deodorizing amount does not depend on the exposure amount of the vitreous deodorant. For this reason, in the long term, it is sufficient that a small amount is exposed on the surface of the paper, and even if the content exceeds the above range, an increase in deodorizing amount cannot be expected.

  As described above, the deodorizing paper of the first embodiment includes the glassy deodorant 2 between the fibers 1 constituting the paper, and the deodorizing paper of the second embodiment is made of paper. The deodorizing layer 3 containing the glassy deodorant 2 is formed on the surface. In the case of the first embodiment, deodorized paper can be obtained by a method of impregnating paper in a slurry containing a vitreous deodorant and then squeezing and drying. In the case of the second embodiment, the deodorized paper can be obtained by a method in which a glassy deodorant is contained in a binder and applied and sprayed. In the case where a glassy deodorant is carried on the surface of the paper as in the deodorant paper of the second embodiment, the glassy deodorant that is buried in the fiber and does not contribute to deodorization is reduced. Therefore, the deodorizing effect can be further enhanced. Examples of the binder include the following. Acrylic resin, urethane resin, epoxy resin, cellulose resin, alkyd resin, polyamide resin, styrene resin, xylene resin, styrene resin, amino resin, phenol resin, natural resin, natural resin derivative, petroleum resin, chlorinated rubber, polyvinyl chloride , Vinyl chloride / vinyl acetate copolymer resin, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, chlorinated polypropylene, and the like can be used.

  Alternatively, the above-described deodorizing paper may be laminated, or the above-mentioned deodorizing paper and paper containing no vitreous deodorant may be laminated to obtain a laminated paper having a laminated structure.

  The deodorizing paper of this invention has a function which decomposes | disassembles a malodorous component by the catalytic action of the copper component hold | maintained in the glass of a vitreous deodorizing agent. Unlike the soluble glass, the copper component decomposes the malodorous component by the catalytic action while being retained in the glass, so that the deodorizing effect is maintained over a long period of time and the durability is excellent. Further, since the soluble glass is an acidic glass, it does not have a deodorizing effect on lower fatty acids that are acidic malodors, but the vitreous deodorant in the present invention has a deodorizing effect on malodorous substances such as lower fatty acids and body odor components. .

  The deodorizing paper of the present invention can of course be used as it is, but is suitable for use as a bag for food, a confectionery bag, a shopping bag, a garbage bag, etc. Since the glassy deodorant is harmless to the human body, it can be used as a food packaging bag. Moreover, since it has a deodorizing effect on malodorous substances such as lower fatty acids and body odor components, it can be used as a diaper bag in the field of nursing care. It is also suitable as toilet paper and its core material paper. Furthermore, if it is used as shoji paper, paper, etc., it has the effect of eliminating indoor odors.

  Other uses such as tissue paper, coated paper, non-coated paper, printing paper, drawing paper, laminate paper, pet sheet, shoe box, shoe wrapping paper, clothing wrapping paper, newspaper, separate sheet, cardboard, etc. be able to. In particular, the separate sheet is suitable for use because it is repeatedly used for storage and transportation of food and food containers. Moreover, especially for diapers, the deodorizing effect can be enhanced by holding paper in a sealed container. Since the deodorizing effect is promoted by moisture, it can be used in combination with a simple toilet.

In the above-described embodiment, the vitreous deodorant is used alone, but it can also be used in combination with an inorganic deodorant such as general-purpose silica gel, zeolite, activated carbon, clay mineral, photocatalyst (titanium dioxide). It can also be used with soluble glass containing silver. Such combined use makes it possible to aim at effects such as speeding up the deodorization speed, expanding target gas, and reducing costs. In particular, when used in combination with a simple toilet, the combined use with soluble glass that elutes silver ions can further enhance the antibacterial and deodorizing effects.
Examples of the present invention are shown below. In the table, nd means not detected.

  A glass raw material was prepared so as to have the composition shown in Table 1, and melted, molded, and pulverized in the same manner as general-purpose glass compositions such as bottle glass to produce a glassy deodorant. The obtained glassy deodorant was contained in paper under the conditions shown in Table 2 to obtain deodorized paper. This deodorizing paper was enclosed in a tedlar bag and a deodorizing effect confirmation test was performed. In Table 2, “type of fiber” means “type of main component of fiber constituting paper”. Here, the main component includes the intention to allow other components to be contained within a range that does not interfere with the function of the main component, and does not particularly specify the content ratio of the main component. Occupies the largest content, and preferably includes 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more (including 100%).

Embodiment 1 in Table 2 is one in which a glassy deodorant is added to wood pulp and handsheets are adjusted based on JIS P 8222. Embodiment 2 is a cell roll for waste paper (100%). This is spray-coated on both sides using a system binder. All were cut to 100 × 100 mm and sealed with malodorous components in a Tedlar bag. In addition, the contents shown in Table 2 indicate the contents shown in the specification (Embodiment 1: ○ mass, Embodiment 2: ○ mass% / m ² ), and correspond to the conditions in the experiment. The sample to be cut was cut.

(Example A)
The papers of Experimental Examples 1 to 11 and 13 to 22 in Table 2 were sealed with malodorous components in a 1 L Tedlar bag, and the malodor concentration in the bag with the elapsed time was measured at room temperature. Hydrogen sulfide and methyl mercaptan were measured with a gas chromatograph, propionic acid and isovaleric acid were measured with a gas detector tube, and trans-2-nonenal was measured with a high performance liquid chromatograph. As a comparison, a glassy deodorant composed of the soluble glasses 1 to 3 shown in Table 3 was produced, and a paper with a glassy deodorant content of 1% by mass was prepared in the first embodiment. Cut out. In addition, the blank which does not contain a copper component corresponds to Experimental Examples 6 and 16. As a result, as shown in Table 4, it was confirmed that there was a deodorizing effect against any offensive odor.

(Example B)
The papers of Experimental Examples 5 and 12 in Table 2 were sealed with malodorous components in a 1 L Tedlar bag, and the malodor concentration in the bag with the elapsed time was measured at room temperature with a gas chromatograph. As a comparison, a vitreous deodorant composed of the soluble glasses 2 to 4 shown in Table 3 was produced, and 1% by mass of paper was prepared in the first embodiment, and cut similarly. As a result, as shown in Table 5, it was confirmed that the soluble glass reached the deodorization limit, whereas Experimental Example 5 had a large total deodorization amount. The deodorizing limit of the soluble glass is determined according to the exposure amount, whereas the vitreous deodorant containing a copper component shows a catalytic action, so that even if a small amount is exposed, the total deodorizing amount can be expected. . However, the glass changes continuously depending on the composition, and the effect also changes continuously from the catalytic reaction to the adsorption reaction of the soluble glass. Since Experimental Example 12 had a composition with reduced durability, it exhibited an adsorption reaction like the soluble glass, and it was confirmed that the deodorization limit was reached.

(Example C: Basic characteristics and decomposition action of glassy deodorant)
D ₅₀ = 4.2 μm ground glass 1g consisting of composition number 6 in Table 1 and methyl mercaptan were sealed in a 5 L Tedlar bag, and methyl mercaptan and dimethyl disulfide in the bag over time were measured with a gas chromatograph at room temperature. did. Moreover, the same operation was performed as a blank, without a glassy deodorant. In addition, it was confirmed in advance by a gas chromatograph mass spectrometer that the gas components present in the bag were only these two components. As a result, as shown in FIG. 3, it was confirmed that the vitreous deodorant of the present invention has an action of decomposing methyl mercaptan and generating dimethyl disulfide. The basic characteristics of the vitreous deodorant are naturally retained even when incorporated in paper.

(Example D: Basic characteristics of glassy deodorant / radical generation)
D ₅₀ = 0.1 mol·L ⁻¹ phosphate buffer solution of pH = 7.4 with respect to 200 mg of the glass composed of the soluble glass 1 of composition numbers 6 and 9 and table 3 of Table 1 ground to 5.0 μm 200 μL was added. Thereto, 10 μL of 9.2 mol·L ⁻¹ DMPO (manufactured by LABOTEC, LM-2110) was added and shaken. Shake was stopped 10 seconds, 1 minute, and 5 minutes after DMPO addition, and only the solution was collected with a hematocrit tube, and ESR (manufactured by JEOL Ltd., FR-30, X band) measurement was performed. Moreover, the thing except glass was made into the blank. All were performed at room temperature under fluorescent light. This technique corresponds to the spin trap method, which is a general technique for measuring radicals, and spin adducts are generated when DMPO captures radicals. This product (DMPO-OH) was detected by ESR. The unit of the detected value is a peak area value ratio (area single / area manganese, S / M) with respect to the reference material Mn ²⁺ . The results are shown in Table 6. The composition No. 6 glass was confirmed to produce DMPO-OH, whereas the composition No. 9 and the soluble glass 1 only showed a background value as in the blank. It was confirmed that the vitreous deodorant of the present invention has a high possibility of generating radicals.

(Example E: Basic characteristics of glassy deodorant and suppression of catalyst deterioration)
D ₅₀ = 4.2 μm crushed glass of composition number 6 in Table 2 0.1 g and CuO reagent (average particle size 4 μm) 0.1 g each was sealed in a 1 L Tedlar bag at room temperature with time The methyl mercaptan concentration in the bag was measured with a gas chromatograph. The initial concentration of methyl mercaptan was 55 ppm and repeated up to 10 times. Moreover, the same operation was performed without glass as a blank. As a result, as shown in Table 7, the deodorizing effect of the CuO reagent is reduced with repetition. This is a generally known catalyst deterioration (sulfur adsorption) of CuO. On the other hand, it was confirmed that the glass maintained the deodorizing effect and was highly sustainable. Although elucidation of this mechanism remains, it has been confirmed that catalyst degradation is suppressed by vitrification. When the glass surface at this time was analyzed by XPS (manufactured by ULVAC-PHI Co., Ltd., PHI 5000 VersaProbe), as shown in Table 8, it was confirmed that there was certainly no sulfur adsorption after deodorization. The basic characteristics of the vitreous deodorant are naturally retained even when incorporated in paper.

1 fiber 2 glassy deodorant 3 deodorant layer

Claims (5)

A deodorizing paper carrying a glassy deodorant between fibers constituting the paper or on the surface of the paper,
This glassy deodorant consists of an alkali-alkaline earth-borosilicate glass containing a copper component or an alkali-alkaline earth-silicate glass containing a copper component,
A deodorizing paper characterized by having a function of decomposing malodorous components by the catalytic action of a copper component held in glass.   The deodorizing paper according to claim 1, wherein the content of the vitreous deodorant carried between the fibers constituting the paper is 0.1 to 10% by mass. Deodorant sheet according to claim 1, wherein the content of the vitreous deodorant is carried on the surface of the paper, was 0.1-5 g / m ^2. The deodorizing paper according to any one of claims 1 to 3, wherein the glassy deodorant is a powder having a D _{96 of} 40 µm or less.   A deodorizing paper, wherein the deodorizing paper according to any one of claims 1 to 4 is laminated or laminated with a paper not containing a glassy deodorant to form a laminated structure.