WO2006112128A1 - 消臭抗菌繊維製品 - Google Patents
消臭抗菌繊維製品 Download PDFInfo
- Publication number
- WO2006112128A1 WO2006112128A1 PCT/JP2006/302817 JP2006302817W WO2006112128A1 WO 2006112128 A1 WO2006112128 A1 WO 2006112128A1 JP 2006302817 W JP2006302817 W JP 2006302817W WO 2006112128 A1 WO2006112128 A1 WO 2006112128A1
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- WIPO (PCT)
- Prior art keywords
- mineral
- sheet
- metal
- antibacterial
- cantalinite
- Prior art date
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Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H5/00—Special paper or cardboard not otherwise provided for
- D21H5/22—Fungicidal, bactericidal, insecticidal, disinfecting, antiseptic, or corrosion-inhibiting paper antistatic, antioxygenic paper
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
- A61L2/23—Solid substances, e.g. granules, powders, blocks, tablets
- A61L2/238—Metals or alloys, e.g. oligodynamic metals
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/01—Deodorant compositions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
Definitions
- the present invention relates to a deodorant antibacterial fiber product.
- the present invention also relates to an absorbent article provided with the deodorant antibacterial fiber product.
- zeolites are known as substances having an antibacterial action in addition to a deodorizing action.
- One method of supporting the zeolite on the sheet is to knead it into the used fat. However, since only part of the zeolite is exposed on the surface, the efficiency is poor.
- zeolite when adhering to the surface of a sheet, zeolite has good adhesion to fiber materials such as pulp V. Therefore, it is difficult to carry a large amount on a sheet that is strong in fiber materials such as wet papermaking paper. is there. Moreover, even if blended in a large amount, an efficient deodorizing and antibacterial effect cannot be exhibited. In other words, the deodorizing and antibacterial effect cannot be effectively exhibited even with a small amount.
- the present invention provides a deodorant antibacterial fiber product including a cantalinite-like mineral containing a metal having antibacterial properties, a clay mineral, softwood bleached kraft pulp and hardwood bleached kraft pulp.
- the deodorizing antibacterial fiber product in the form of a sheet is disposed between the top sheet and the absorbent body, between the absorbent body or between the absorbent body and the back sheet.
- Absorbent articles are provided.
- FIG. 1 is a perspective view showing an embodiment of a deodorant antibacterial fiber product of the present invention.
- FIG. 2 is a perspective view showing a state where an absorbent body is coated with the deodorant antibacterial fiber product shown in FIG. 1.
- FIG. 3 is a cross-sectional view in the width direction of an absorbent pad produced in Examples and Comparative Examples.
- the deodorant antibacterial fiber product of the present invention is one in which a deodorant antibacterial agent is attached to a fiber material.
- the deodorizing antibacterial agent includes a cantalinite-like mineral containing a metal having antibacterial properties (hereinafter referred to as a metal-substituted cantalinite-like mineral) and a clay mineral.
- the metal-substituted canthalinite-like mineral is obtained by replacing the metal element in the cantalinite-like mineral with a metal element having antibacterial properties.
- Textile materials include softwood bleached kraft pulp (hereinafter also referred to as NBKP) and hardwood bleached kraft pulp (hereinafter also referred to as LBKP).
- the cantalinite-like mineral has a structure similar to that of an aluminosilicate compound.
- the cantalinite-like mineral is JCPDS (joint 'committy' on 'know- ment, diffr. Standers) No. 20—379, 20—743, 25—776, 25—1499, 25—1500 30-1170, 31-1272, 34-176, 35-479, 35-653, 38-513, 38-514, 38-515, and 45-1373
- Metal-substituted cantalinite-like minerals have a wide deodorant spectrum, and various malodors such as alkaline odors such as ammonia, amine and pyridine, acidic odors such as lower fatty acids and mercabtan, and other esters, ketones and aldehydes. It has been found by the present inventors that the present invention has a good deodorizing action against bad odor, which is a characteristic odor. It was also found to have a high antibacterial effect. In other words, it was found that the metal-substituted canthalinite-like mineral exhibits a high deodorizing and antibacterial action even when the amount used is small.
- the metal-substituted canthalinite-like mineral particles have a tetrapod-like shape, a confetti-like shape, or a u-like shape, and due to the shape, the adhesion to fiber materials such as pulp may be extremely good. found.
- the present inventors have made various studies.
- the metal-substituted canthalinite-like mineral in combination with clay minerals, the metal-substituted cantalinite-like mineral is used as a fiber material. It has been found that even if it is attached to the material, it is possible to prevent the deodorizing and antibacterial action from decreasing, and the present invention has been completed.
- the deodorant antibacterial fiber product of the present invention can attach a large amount of metal-substituted cantalinite-like mineral, and the fiber product exhibits extremely high deodorant ability and antibacterial ability.
- the textile product exhibits sufficiently high deodorizing ability and antibacterial ability.
- the amount of the clay mineral in the deodorant antibacterial fiber product of the present invention is 1 to 30% by weight, particularly 1 to LO weight% based on the force fiber material depending on the type of the clay mineral. Further, the ability to prevent metal from deteriorating the deodorizing and antibacterial action of the ncrinite-like mineral is also preferable.
- the clay mineral for example, zeolite, sepiolite, bentonite or the like which is a silicate other than the cantalinite-like mineral can be used.
- zeolite from the viewpoint that the deodorizing and antibacterial effect of the metal-substituted cantalinite-like mineral is high.
- the amount of clay mineral used is also related to the amount of metal-substituted canthalinite-like mineral deposited.
- the amount of the clay mineral is 100 to 800% by weight, particularly 200 to 600% by weight, based on the amount of the metal-substituted cantalinite-like mineral. It is preferable from the viewpoint of preventing the decrease.
- the adhesion amount of the metal-substituted cantalinite-like mineral to the fiber material in the deodorant antibacterial fiber product of the present invention can be adjusted over a wide range depending on the specific use of the fiber product.
- the content may be 0.01 to 20% by weight and the special content 0.2 to 10% by weight with respect to the fiber material.
- the fiber material in the deodorant antibacterial fiber product of the present invention contains NBKP and LBKP. By using a combination of both, the fiber product is imparted with appropriate paper strength, Softness can be imparted.
- NBKP When only NBKP is used without using LBKP, the deodorized antibacterial fiber product tends to harden.
- the product is manufactured by incorporating the fiber product into a processing machine, there is a possibility that trouble may occur.
- LBKP is used without using NBKP
- the strength of the deodorant antibacterial fiber product tends to decrease, and there is a possibility that troubles such as running out of paper may occur in the beam processing machine.
- the weight ratio of NBK PZLBKP is preferably 95Z5 to 50Z50, and more preferably 955 to 6040.
- the deodorized antibacterial fiber product of the present invention is produced by wet papermaking, from the viewpoint of successfully making the papermaking, the beating state of the blended pulp of NBKP and LBKP is controlled, and the Canadian standard filtered water of the blended pulp is used.
- the degree JIS P8121, hereinafter also referred to as CSF
- CSF degree (JIS P8121, hereinafter also referred to as CSF) is preferably 400 to 600 ml, particularly 450 to 600 ml.
- the fiber material in the deodorant antibacterial fiber product of the present invention may be composed of only NBKP and LBKP, or may contain rayon in addition to these.
- a small amount of heat-fusible fibers made of thermoplastic resin can also be used.
- a wet paper strength agent to the deodorant antibacterial fiber product of the present invention.
- high wet strength can be imparted to the textile.
- Increasing the wet strength of the textile product is advantageous from the viewpoint that, when the textile product is used as a constituent material of an absorbent article such as a disposable diaper, it is difficult to break even if the textile product is wet by urine or the like. It is.
- increasing the wet strength means increasing the strength in the dry state. Therefore, troubles are less likely to occur when a product is manufactured by incorporating the deodorant antibacterial fiber product of the present invention into a processing machine.
- the tensile strength of MD in the dry state is preferably a high value of 4 OOcNZ 25 mm or more.
- the method for measuring the tensile strength will be described in the examples below.
- the wet paper strength agent for example, polyamidoamine and epichlorohydrin resin can be used.
- the wet paper strength agent is preferably blended in an amount of 0.01 to 5% by weight, particularly 0.1 to 2.0% by weight, based on the fiber material, from the viewpoint of obtaining sufficient wet strength.
- composition formula (1) As the metal-substituted cantalinite-like mineral, it is preferable to use one represented by the following composition formula (1).
- M (l) represents a metal having antibacterial properties
- M (2) represents one or more elements selected from the group consisting of Na, K, and H force
- R represents Na, K, Ca
- Mg Represents one or more elements selected from the group consisting of
- Q is one or more elements selected from the group consisting of CO, SO, NO, OH and CI
- M (l) is preferably Ag, Zn or Cu because of its high deodorizing ability against sulfur-containing malodors, and particularly preferably Ag.
- M (l) may be one type or a combination of two or more types.
- sM (l) O is described separately for each term corresponding to each element. For example, when M (l) force consists of metal elements D and D ', sM (l) O is s D O -s D O (where xl +
- M (2) is preferably Na and Z or H from the viewpoint of high deodorizing ability and economical efficiency.
- R is preferably one or more metal elements selected from the group consisting of Na, Ca and Mg, and more preferably Na.
- Q is preferably CO and Z or NO from the viewpoint of ease of particle shape control.
- s is preferably 0 ⁇ s ⁇ 2, and more preferably 0 ⁇ s ⁇ l, from the viewpoint of high deodorizing ability and economical efficiency.
- t is preferably 0 ⁇ t ⁇ 2, more preferably 0 ⁇ t ⁇ 1, from the viewpoint of maintaining a good pH of the aqueous dispersion of metal-substituted cantalinite-like mineral (1 wt% aqueous dispersion described later).
- s + ti preferably ⁇ 0.5 to 1.8, and more preferably ⁇ 0.6 to 1.5. From the viewpoint of developing a high deodorizing ability, it is preferably 0.5 ⁇ u ⁇ 5, more preferably 0.5 ⁇ u ⁇ 4.
- V is preferably 0 ⁇ ⁇ 1.5, more preferably 0 ⁇ v ⁇ 1, from the viewpoint of ease of particle shape control.
- w is the content (molar ratio) of water contained in the metal-substituted canthalinite-like mineral and varies depending on the form of the metal-substituted canthalinite-like mineral, for example, in the form of powder or slurry.
- X and y, and m and n are arbitrarily determined depending on the combination of M (l) and O, and the combination of R and Q, respectively.
- metal-substituted Kantarinaito like mineral in its specific surface area forces lm 2 / g or more 70m 2 / g less der Rukoto is preferably instrument L ⁇ 65m 2 is further preferably a Zg instrument 30 ⁇ 65M 2 Zg More preferably it is. If the specific surface area is within this range, an antibacterial metal can be appropriately fixed or supported, and an excellent deodorizing ability against sulfur-containing malodors can be exhibited.
- the metal-substituted canthalinite-like mineral preferably has a pH of 1% by weight aqueous dispersion of 7 or more, more preferably 8 or more. More preferably, it is 9 or more.
- the pH of the 1% water dispersion of metal-substituted cantalinite-like minerals can be determined by the method described below.
- the M (l) component exhibits deodorizing ability by adsorbing a sulfur-containing malodor. Therefore, it is preferable that a large amount of M (l) component is present in the vicinity of the surface of the metal-substituted canthalinite-like mineral from the viewpoint of developing an excellent deodorizing power.
- the surface concentration of the M (1) component depends on the molar ratio of the M (l) component atom to the Si atom [M (l) ZSi] or the molar ratio of the M (l) component atom to the Al atom measured by ESCA [M (1) ZA1].
- M (l) / Si is preferably 0.021 or more, more preferably 0.040 or more. Further, M (1) / A1 is preferably 0.025 or more, more preferably 0.040 or more.
- the measurement by ESCA can be performed using ESCA-1000 manufactured by Shimadzu Corporation after forming the sample into a thin piece with a press. Measure the elements on the sample surface [M (1) component atoms, Si, Al], and obtain the surface atom concentration ratio (molar ratio) from the peak area of the obtained elements.
- Metal-substituted canthalinite-like minerals have an average particle size of 0.1-1000 ⁇ m, especially 0.4-600 / ⁇ ⁇ , especially 1-100 / ⁇ ⁇ , which has a high deodorizing rate. Further, the point power at which powder flowability is good is preferable.
- the average particle diameter is measured at a relative refractive index of 1.16 using, for example, a laser diffraction / scattering particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.).
- the metal-substituted canthalinite-like mineral may be amorphous or crystalline. From the viewpoint of improving the deodorizing ability of sulfur-containing malodors, it is preferably crystalline.
- the metal-substituted canclinite-like mineral can be obtained as an aggregate of needle-like crystals, plate-like crystals, columnar crystals, etc. depending on the production conditions. Further, these secondary aggregates may be used, in which the crystals aggregate to form a spherical, tetrapod-like, massive aggregate or the like.
- the needle-shaped form means a thickness of 500 nm or less and a length of 2.0 or more in aspect ratio with respect to the thickness.
- a plate-like form is one having a thickness of 300 nm or less and a plate diameter of 2.0 or more in terms of the aspect ratio with respect to the thickness.
- the columnar form is one having a thickness of 50 nm or more and a length of 1.0 to less than 2.0 with respect to the thickness.
- the metal-substituted canthalinite-like mineral has, for example, the composition of anhydride: aM 0 -A1 O -bSiO
- CR Q (wherein M represents Na and Z or K, R represents a group consisting of Na, K, Ca and Mg m n
- the raw aluminosilicate 100 8 uses 0 ⁇ 3001116 (0 ⁇ 3001116/100 8 ) acid per 1 ⁇ It is preferably obtained by subjecting to an acid treatment step and an ion exchange step with antibacterial ions.
- M is preferably Na.
- aM O is a'Na
- R is preferably one or more elements selected from the group consisting of Na, Ca and Mg, and more preferably Na.
- Q is preferably CO and Z or NO. a is preferably 0.
- 5 ⁇ a ⁇ 2. 5 is more preferable, and 0.5 ⁇ 5 ⁇ a ⁇ 2.
- Bi preferably ⁇ , 0.5 ⁇ b ⁇ 5, more preferably 0.5 ⁇ b ⁇ 4.
- c is preferably 0 ⁇ C ⁇ 1.5, more preferably 0 ⁇ c ⁇ l.
- m and n are arbitrarily determined according to the combination of R and Q.
- the specific surface area of the raw material aluminosilicate is preferably about the same as that of the metal-substituted cantalinite-like mineral.
- the average particle size is preferably about the same as that of the metal-substituted cantalinite-like mineral.
- the form is not particularly limited, but for example, the same form as the metal-substituted cantalinite-like mineral is preferable.
- the method for producing the raw material aluminosilicate is not particularly limited. For example, reacting alumina raw material and silica raw material in an alkaline solution in the presence of CO 2 —, SO 2 —, NO—, CI—, etc.
- alumina raw material examples include aluminum oxide, aluminum hydroxide, sodium aluminate and the like. Sodium aluminate is particularly preferable.
- silica raw material examples include key sand, key stone, water glass, sodium keyate, and silica sol. Water glass is particularly preferable.
- clay minerals such as kaolin, montmorillonite, bentonite, my strength, and tar, and aluminosilicate minerals such as mullite may be used.
- Examples of the material include carbon dioxide, sodium carbonate, potassium carbonate, sodium potassium carbonate, calcium carbonate, magnesium carbonate and the like. Sodium carbonate is particularly preferred.
- Examples of raw materials for so 2 include sulfuric acid, sodium sulfate, potassium sulfate, and sodium sulfate
- Examples include lithium.
- sulfuric acid and sodium sulfate are suitable.
- Examples include nitric acid, sodium nitrate, and potassium nitrate. Nitric acid and sodium nitrate are particularly suitable.
- Examples of the raw material for cr include hydrochloric acid, sodium chloride salt, potassium salt salt, and the like. In particular, hydrochloric acid and sodium chloride are preferred.
- Examples of the alkali of the alkaline solution include oxides such as sodium hydroxide and potassium oxide; hydroxides such as sodium hydroxide and potassium hydroxide; carbonates such as sodium carbonate, potassium carbonate and potassium carbonate. Salt; bicarbonates such as sodium bicarbonate and potassium bicarbonate can be used.
- oxides such as calcium oxide and magnesium oxide; hydroxides such as calcium hydroxide and magnesium hydroxide; carbonates such as calcium carbonate, magnesium carbonate and dolomite; calcium hydrogen carbonate and magnesium hydrogen carbonate etc.
- a hydrogen carbonate salt or the like may be used.
- the raw material aluminosilicate can be obtained by blending the above-mentioned various compounds at a predetermined ratio and mixing and reacting them.
- the mixing ratio is appropriately determined according to the composition of the desired raw material aluminosilicate to be obtained.
- the charging ratio of a component that is a raw material of the raw material aluminosilicate is M based on the constituent elements of each component.
- the molar ratio of M 2 O / SiO is preferably 0.
- R Q / SiO ⁇ to preferably ⁇ or 0.001
- n 2-100 is between 0 and 05 to 80, and HO / M is preferably ⁇ or 0.00.
- the reaction temperature at the time of producing the raw material aluminosilicate is preferably 15 from the viewpoint of increasing the crystallinity of the raw material aluminosilicate, stabilizing the form, and reducing the chemical and pressure-resistant loads on the reaction vessel. ⁇ 300 ° C, more preferably 60-150 ° C, and even more preferably 80-130 ° C.
- the reaction time is preferably 2 hours or more and 48 hours or less from the viewpoint of complete crystallization reaction.
- the raw material aminosilicate is usually obtained as an aqueous dispersion (slurry).
- the solid content concentration of the aqueous dispersion is preferably 0.1 to 50% by weight.
- the obtained raw material aluminosilicate is subjected to an acid treatment using 0 to 300 meq (0 to 300 meq Zl00 g) of acid per 100 g of the raw material aluminosilicate.
- the acid treatment is performed to adjust the pH of the slurry when the M (l) component is fixed or supported on the raw aluminosilicate by ion exchange. At that time, it is preferable to adjust the pH of the slurry to pH 7 or less from the viewpoint of the expression of ion exchange properties of the M (l) component. Acid treatment is also performed to adjust the specific surface area.
- the case where the acid treatment is performed using the acid of OmeqZlOOg means the case where the acid treatment is not performed.
- the raw material aminosilicate may not be subjected to acid treatment.
- hydrochloric acid or nitric acid which is preferably a strong acid such as hydrochloric acid, sulfuric acid or nitric acid.
- the acid treatment is performed by adding the aqueous solution containing the acid to the raw material aluminosilicate gradually or all at once and bringing the acid into contact with the raw material aluminosilicate.
- the addition rate is preferably from 0.01 to: LOOmlZ, more preferably from 0.1 to LOmlZ, per 100 g of raw material aluminosilicate.
- the raw material aluminosilicate is preferably made into a slurry.
- the solid content concentration of the slurry is preferably 1 to 50% by weight from the viewpoint of ensuring the fluidity of the reaction mixture and preventing the unevenness of the acid treatment to improve the treatment efficiency.
- the temperature during the acid treatment is preferably 60 to 150 ° C, more preferably 80 to 120 ° C, from the viewpoint of improving the specific surface area and reducing the chemical and pressure load on the reaction vessel. is there.
- the acid treatment may be performed with appropriate stirring.
- the time for the acid treatment is preferably 0.01 to LOO time, and more preferably 0.1 to 10 hours, when the acid and raw material aluminosilicate are brought into contact with each other.
- the reaction mixture is preferably suitably aged at, for example, 60 to 150 ° C. for about 0.1 to 1 hour.
- the raw material aluminosilicate after acid treatment is ion-exchanged with ions of a metal having antibacterial properties.
- the raw material aluminosilicate having a desired specific surface area may be ion-exchanged as it is without acid treatment.
- ion exchange for example, the raw material aluminosilicate after acid treatment is suspended in water, and a compound containing the metal (hereinafter referred to as a metal-containing compound) or an aqueous solution of the compound is added thereto, or an aqueous solution of the metal-containing compound. It can be carried out by immersing the raw material aluminosilicate in the inside.
- the raw material aluminosilicate does not have to be ion-exchanged after the acid treatment.
- the metal-containing compound is allowed to coexist during the acid treatment, the raw material aluminosilicate is acid-treated and ion-exchanged. Can be performed simultaneously.
- the metal-containing compound is not particularly limited as long as it is a water-soluble metal-containing compound containing a desired metal. For example, nitrates, sulfates, salts, and the like containing a desired metal can be used. .
- the ion exchange is usually performed with the raw material aminosilicate suspended in water and stirring.
- the solid content concentration of the aqueous suspension of the raw aluminosilicate is preferably 1 to 50% by weight.
- the temperature at the time of performing ion exchange is not particularly limited. Preferably it is 20-120 degreeC, More preferably, it is 80-110 degreeC.
- the ion exchange time is preferably 0.01 to 2 hours, more preferably 0.02 to 1 hour, after the raw material aluminosilicate is brought into contact with the metal-containing compound.
- the amount ratio of the raw material aluminosilicate to the metal-containing compound in the ion exchange is preferably 0.1 to 30 parts by weight, more preferably 0.2 to 100 parts by weight of the raw material aluminosilicate. ⁇ : LO parts by weight, more preferably 0.5 to 5 parts by weight.
- the reaction mixture is preferably aged as appropriate for about 0.1 to 10 hours at 60 to 150 ° C, for example.
- the metal component in the metal-containing compound is most preferably fixed or supported on the cantalinite-like mineral by ion exchange as described above.
- metal components in metal-containing compounds can be It may be fixed or supported on a ncrinite-like mineral.
- ion exchange ion exchange
- raw material aluminosilicate is treated with impurities, etc. You may wash
- the washing can be performed, for example, by filtering and washing the aqueous suspension of the raw aluminosilicate.
- the filter used for filtration is not specifically limited, For example, a Nucci type, a filter press type, etc. can be used.
- M represents one or more elements selected from the group consisting of Na, K and H
- R represents one or more elements selected from the group consisting of Na, K, Ca and Mg
- Q represents CO, SO, N
- s is 0 ⁇ s ⁇ 1
- the second metal-substituted canthalinite-like mineral corresponds to a cantalinite-like mineral represented by the composition formula (2) in which a part of M is substituted with an antibacterial metal.
- the substitution amount of the metal having antibacterial properties in the cantalinite-like mineral represented by the composition formula (2) is 0.1 to 30% by weight, particularly 0%, from the viewpoint of expression of desired deodorizing ability and antibacterial ability and economy. It is preferably 1 to 10% by weight.
- the amount of these metals can be measured by fluorescent X-ray measurement.
- the second metal-substituted canthalinite-like mineral it is preferable that aluminum contained in the second metal-substituted cantalinite-like mineral is eluted by an acid and a part thereof is in an amorphous state. aluminum As a result of elution, a large number of micropores are formed in the second metal-substituted canthalinite-like mineral, and the deodorizing ability is further enhanced. The elution of aluminum by acid will be described later.
- the second metal-substituted Kantarinaito like mineral, a specific surface area of 70 ⁇ 800m 2 / g, especially 80 ⁇ 600M 2 Zg, especially 100 to 500 m 2 that force moderate deodorizing rate and wider deodorant is Zg I also like the ability to express the spectrum.
- the second metal-substituted canthalinite-like mineral preferably has an acid amount of 20 meqZl00g or more, particularly lOOmeqZlOOg or more, particularly 170 meq / 100g or more, from the viewpoint of improving the deodorizing ability of the alkaline malodorous gas.
- “Acid amount” refers to the total amount of acid sites of the second metal-substituted canthalinite-like mineral. The amount of acid was determined by stirring 0.5 mL of the sample in 1 OO ml of 0.1 mol OlOHZl NaOH aqueous solution for 1 hour, then centrifuging the resulting sample suspension (lOOOO rpm X 5 minutes), and collecting 25 ml of the supernatant. NaOH consumed by titration with 0. OlmolZl of HNO
- the average particle size of the second metal-substituted canthalinite-like mineral is preferably 1 to 500 m, more preferably 1 to 300 m, and even more preferably 1 to LOO m. Within such a range, an appropriate deodorization rate can be obtained, and the handleability can be improved.
- M is preferably Na and Z or H from the viewpoint of high deodorizing ability and economy.
- R is M
- Na is preferred.
- Q is preferably CO or NO from the viewpoint of ease of particle shape control.
- s is preferably 0 ⁇ s ⁇ 0.5.
- V is high
- w is the water content (molar ratio) in the precursor
- ml and nl are arbitrarily determined according to the combination of R and Q.
- the second metal-substituted cantalinite-like mineral is obtained, for example, by subjecting a raw material aluminosilicate to an acid treatment.
- a cantalinite-like mineral is formed, and the resulting cantalinite-like mineral is suspended in water, and an aqueous solution of a water-soluble salt of a metal having antibacterial properties is added thereto for ion exchange.
- it can also be suitably produced by performing ion exchange in the presence of an antibacterial metal water-soluble salt during acid treatment of the raw material aluminosilicate.
- the raw material aluminosilicate used for the second metal-substituted cantalinite-like mineral is represented by the following composition formula (3).
- alumina raw material and silica raw material are mixed with CO 2 SO.
- a strong acid such as hydrochloric acid, sulfuric acid or nitric acid
- hydrochloric acid and nitric acid are preferably used.
- A1 also partially elutes.
- the degree of acid treatment may be appropriately adjusted so that the finally obtained second metal-substituted cantalinite-like mineral has desired properties.
- the acid treatment is performed by adding the aqueous solution containing the acid gradually or all at once to the raw material aluminosilicate and bringing the acid into contact with the raw material aluminosilicate.
- the addition rate is preferably from 0.01 to LOOmlZ, more preferably from 0.1 to LOmlZ, per 100 g of raw material aluminosilicate.
- the cantalinite-like mineral obtained by acid treatment of the raw material aluminosilicate is preferably aged at 60 to 150 ° C for about 0.1 to L0 hours.
- the slurry is then filtered and washed with water to remove excess ionic components.
- the cantalinite-like mineral separated by filtration is suspended in water, and an aqueous solution of a water-soluble metal salt having antibacterial properties is added and aged for a predetermined period of time while heating to a predetermined temperature. This gives the desired second metal-substituted canthalinite-like mineral.
- the deodorant antibacterial fiber product of the present invention can take various forms depending on its production method.
- the deodorant antibacterial fiber product of the present invention may take a form such as a sheet form, a fragmented form thereof, a granular form, or a three-dimensional molded article form.
- These forms can be obtained by producing the deodorant antibacterial fiber product of the present invention by a wet method.
- the sheet When the deodorant antibacterial fiber product of the present invention is in the form of a sheet, the sheet may be in the form of a single layer containing a metal-replaced cantalinite-like mineral, or a laminated sheet in which a plurality of sheets are stacked. Form may be sufficient.
- the sheet When in the form of a single-layer sheet, the sheet is produced by a wet papermaking method using a slurry containing fiber material and metal-substituted cantalinite-like mineral particles as raw materials.
- a laminated sheet an example of the sheet is a sheet having the form shown in FIG.
- the deodorized antibacterial fiber product 1 shown in FIG. 1 has two rectangular pulp sheets of the same size, that is, between the first pulp sheet 2 and the second pulp sheet 3, than these pulp sheets 2 and 3. This is a laminated sheet in which a rectangular inner layer sheet 4 having a short length in the width direction is interposed.
- the inner layer sheet 4 is a sheet of fiber material containing particles of metal-substituted cantalinite-like mineral, and this sheet is the same as the single-layer sheet described above.
- Inner layer sheet 4 is a mixed paper of metal-substituted cantalinite-like minerals, and is sandwiched between two pulp sheets 2 and 3 at the center in the width direction. The inner layer sheet 4 and the pulp sheets 2 and 3 are laminated by papermaking.
- the side portions la and lb of the deodorant antibacterial fiber product 1 are not provided with the inner sheet 4 over the entire length direction, and the two side sheets are laminated with two pulp sheets 2 and 3. It is a two-layer structure part.
- the ends on both sides of the deodorant antibacterial fiber product 1 are sealed to prevent the metal-substituted cantalinite-like mineral from falling off the side ends.
- the width of the side portions la and lb is preferably 0.1 to 20 cm, more preferably 1 to 6 cm, to sufficiently prevent the metal-substituted cantalinite-like mineral from falling off and to fully exhibit the functions of the metal-substituted cantalinite-like mineral.
- the point power to make is also preferable.
- the fiber material sheet containing the metal-substituted cantalinite-like mineral (that is, the single-layer sheet and the inner-layer sheet described above) is made from the slurry containing the fiber material and the metal-substituted cantalinite-like mineral particles.
- a flocculant to the slurry.
- flocculants include polyacrylamide and acrylic (methacrylic). A copolymer (molecular weight 5 to 50 million) is preferably used.
- the flocculant is blended in an amount of 0.01 to 0.04% by weight, particularly 0.01 to 0.035% by weight, based on the fiber material.
- strength of the deodorant antimicrobial fiber product of this invention is also preferable.
- the amount of the metal-substituted cantalinite-like mineral in the slurry is preferably 0.1 to: L0% by weight, particularly 0.5 to 5.0% by weight, based on the fiber material.
- the amount of clay mineral is preferably 0.1 to 30% by weight, particularly 0.1 to L0% by weight, based on the fiber material.
- the flocculant is preferably added from the viewpoint of increasing the adhesion amount of metal-replaced cantalinite-like mineral and clay mineral to the fiber material. Te 0.001 to 1.0 wt 0/0, and particularly preferably 0.001 to 0.04 wt%.
- the amount of wet paper strength agent is preferably 0.1 to 5% by weight, in particular 0.1 to 2.0% by weight, based on the fiber material.
- the concentration of the fiber material in the slurry is preferably 0.5 to 5.0% by weight, particularly 1.0 to 3.0% by weight.
- the adhesion rate of the metal-substituted cantalinite-like mineral in the sheet obtained by wet papermaking is 25% or more, especially 50% or more depending on the selection of the flocculant. It can be a high value. The reason for this is largely due to the shape of the metal-substituted canthalinite-like mineral, as described above.
- the sheet preferably has a basis weight of 10 to 100 gZm 2 , particularly 13 to 70 gZm 2 .
- the deodorized antibacterial paper product of the present invention is in the form of a sheet, it can be used by chopping it into small pieces.
- a broken-fragmented deodorized antibacterial paper product can be used as a constituent material of an absorber in an absorbent product described later.
- the deodorized antibacterial paper product of the present invention may take a granular or three-dimensional molded product form in addition to a sheet form.
- a granular form it can be obtained by extruding a high-concentration slurry of a fiber material containing a metal-substituted cantalinite-like mineral in a strand form from an extruder and cutting it into a predetermined size.
- a three-dimensional molded product it can be formed into various container shapes such as a bottle shape, a cup shape, and a tray shape.
- Pulp mold method Details are described, for example, in W099Z42661 relating to the earlier application of the present applicant.
- the deodorant antibacterial fiber product of the present invention is effective for deodorizing and antibacterial in various situations.
- the deodorant antibacterial fiber product of the present invention is in the form of a sheet or a broken piece thereof, the constituent materials of absorbent articles such as disposable diapers, sanitary napkins, absorbent pads, wallpaper, sheets, It is useful as an indentation sheet, bag sheet, shoebox sheet, mat, shoe insole, mask, filter, insole sheet for wrapping food.
- the deodorant antibacterial fiber product of the present invention is in the form of beads or pellets, it is useful as a deodorant for pets such as cat sand.
- the deodorant and antibacterial fiber product of the present invention is in the form of a three-dimensional molded product, it is useful, for example, as an antibacterial and deodorant storage case that is formed into a box shape into a box shape.
- the deodorant antibacterial fiber product of the present invention is in the form of a sheet
- the sheet when the sheet is used as a constituent material of an absorbent article, the sheet is used, for example, between a surface sheet and an absorbent body. Or, it can arrange
- the sheet can be coated with an absorbent material such as pulp or superabsorbent polymer to form an absorbent body, and the absorbent body can be used for absorbent articles.
- the surface sheet is disposed on the side facing the user's skin when the absorbent article is used, and is generally liquid permeable.
- the absorber is disposed between the top sheet and the back sheet and is generally liquid retaining.
- the back sheet is disposed on the opposite side of the top sheet, that is, on the side farther from the user's skin, with the absorbent body in between, and is generally water-repellent or liquid-impermeable.
- FIG. 2 shows a state in which an absorbent body of an absorbent product is coated with the deodorant antibacterial sheet of the present invention as an example of applying the deodorant antibacterial sheet of the present invention to an absorbent article.
- the absorbent body 10 is composed of superabsorbent polymer particles and pulp fibers.
- the absorbent body 10 is covered with the deodorizing and antibacterial sheet 1 so that one side la and the other side lb of the deodorizing and antibacterial sheet 1 are overlapped. Under this state, the absorbent body 10 is sandwiched between a front sheet and a back sheet (not shown) to form an absorbent article.
- the deodorant antibacterial sheet 1 is disposed between the top sheet and the absorbent body and between the back sheet and the absorbent body in the absorbent article.
- any part of the absorbent article contains an adsorbent of sulfur compounds such as hydrogen sulfide or mercabtan, which is a typical substance of bad odor, a metal-substituted cantalinite-like material is obtained.
- the combination of metals and sulfur compounds in minerals Since the resulting antibacterial deterioration of the metal is effectively prevented, it is preferable from the viewpoint of durability of the antibacterial property.
- the deodorizing ability of the metal-substituted cantalinite-like mineral is improved.
- a typical example of an adsorbent for sulfur compounds is zinc oxide.
- the adsorbed substance of the sulfur compound can be attached to the deodorizing antibacterial sheet of the present invention, for example, or can be contained in the absorber.
- the obtained raw material aluminosilicate particles had a porous spherical shape in which acicular crystals were assembled.
- the diffraction pattern corresponded to CPDS No. 38-513.
- the obtained raw material aluminosilicate particles are in the form of a double particle and the composition is Na ⁇ ⁇
- the pH of the 1% aqueous dispersion was 10.04.
- the obtained Ag-substituted canthalinite-like mineral was suspended in ion-exchanged water. Furthermore, blended pulp of NBKP and LBKP, synthetic zeolite 4A type (manufactured by Shilton B Mizusawa Chemical Co., Ltd.), wet paper strength agent (Kaimen WS547 Japan PMC Co., Ltd.), polyacrylamide polymer flocculant (Acoflock A95 Mitsui Chemicals Aqua) Polymer Co.) was added and mixed to obtain a slurry. The pruned pulp used was CSF adjusted to 550 ml by beating. The weight ratio of NBKPZLBKP in the blend pulp was 90Z10.
- the concentration of the blended pulp in the slurry is 2%, the concentration of the Ag-substituted canthalinite-like mineral is 2% with respect to the blended pulp, the concentration of zeolite is 5% with respect to the blended pulp, and the concentration of the wet strength agent is The blended pulp was 0.5%, and the polymer flocculant concentration was 0.025% with respect to the blended pulp.
- a deodorized antibacterial paper which is a deodorant antibacterial fiber product.
- the basis weight was 16gZm 2.
- the amount of Ag-substituted canthalinite-like mineral in the deodorized antibacterial paper was 1% with respect to the blended pulp, and the amount of zeolite was 2.5% with respect to the blended pulp.
- the amount of wet paper strength was 0.45% for the blended pulp and the amount of flocculant was 0.018% for the blended pulp.
- the topsheet 11 of Easu Lou nonwoven basis weight 20GZm 2 On one surface of the resulting deodorant antimicrobial paper 12, the topsheet 11 of Easu Lou nonwoven basis weight 20GZm 2, also on the other surface, the basis weight 350GZm 2
- An absorbent body 13 having a particle strength of a superabsorbent polymer having a pulp and a basis weight of 1 20 gZm 2 was arranged, and both sides of the deodorized antibacterial paper 12 and the absorbent body 13 were covered with an absorbent paper 14 having a basis weight of 15 gZm 2 .
- a liquid-impermeable back sheet 15 having a basis weight of 15 gZm 2 was superposed on the back surface of the coated absorbent body 13.
- an absorbent pad having a length of 400 mm and a width of 150 mm was obtained.
- the non-woven fabric, pulp, superabsorbent polymer, absorbent paper, and liquid-impermeable sheet are used in the relief (registered trademark) urine pad (trade name) manufactured by Kao Corporation! The same material was used.
- a deodorized antibacterial paper and an absorbent pad were obtained in the same manner as in Example 1 except that the composition of the slurry was changed to the values shown in Table 1.
- the adhesion rate of the Ag-substituted canthalinite-like mineral was determined.
- the amount of Ag-substituted canthalinite-like mineral contained in the deodorized antibacterial paper was obtained from the measured amount of the Ag deodorized antibacterial paper after wet decomposition and then measuring the amount of Ag with an ICP emission spectrometer.
- the softness was evaluated by (i) measured value of Balta softness and (mouth) sensory evaluation.
- Each measurement 'evaluation method is as follows.
- the compression speed is lOmmZmim.
- Balta softness in the width direction (CD) is the same as the method for measuring Balta softness in the flow direction (MD) by cutting the deodorized antibacterial paper into large pieces of 150 mm in the flow direction and 30 mm in the width direction. Measure with
- test piece of deodorized antibacterial paper cut to 300mm in the flow direction and 200mm in the width direction. Put this test piece in the box so that it is not visible, and let 10 monitors touch the test piece and evaluate the flexibility.
- the test piece of Comparative Example 1 was used as a criterion for flexibility.
- the comparative evaluation is performed with 4 being more flexible than Comparative Example 1, 3 being the same, 2 being hard, and 1 being very hard. When this average value is 3.5 to 4, ⁇ , when it is 2.5 to 3.4, and ⁇ when it is less than 2.4.
- the deodorized antibacterial paper was cut into a strip having a width of 25 mm and a length of 100 mm, and then immediately mounted on a universal compression tensile tester (RTM-25, manufactured by Orientik Ltd.), and the strength at break was measured.
- the measurement conditions were a tensile speed of 300 mmZmin and a specimen gripping interval of 50 mm. Measurements were made in two directions: the machine direction (MD) and the direction perpendicular to it (CD).
- Continuous production was performed on a round net paper machine, and the state was judged. In the case of continuous production, it was evaluated as ⁇ when troubles such as running out of paper or paper dust did not occur, ⁇ when trouble occurred occasionally, and X when trouble occurred every time.
- Absorbent pad assembly line was used for continuous production of absorbent pad and the condition was judged. It was rated as ⁇ when there was no trouble such as running out of paper during transport of deodorant antibacterial paper, production was not interrupted, ⁇ when it was interrupted occasionally, and X when trouble occurred frequently. If the deodorant antibacterial paper has a dry tensile strength (MD) of 400 cNZ25 mm or less, troubles such as running out of paper may occur during processing.
- MD dry tensile strength
- the deodorized antibacterial paper of each example is soft, has sufficient dry tensile strength, and is productive on a paper testing machine. In addition, it can be seen that there is no problem in the workability of the calorie machine. In contrast, the deodorized antibacterial paper of Comparative Example 1 is inferior in softness, and it can be seen that trouble may occur in production with a papermaking tester. Industrial applicability
- the deodorant antibacterial fiber product of the present invention has sufficiently high deodorant ability and antibacterial ability due to the interaction between a cantalinite-like mineral containing a metal having antibacterial properties and a clay mineral.
- the absorbent article provided with the deodorant antibacterial fiber product of the present invention can effectively prevent the generation of malodor and bacteria caused by excrement.
- the paper strength of the deodorant antibacterial fiber product of the present invention is adjusted by using the above cantalinite-like mineral and viscosity mineral together with softwood bleached kraft pulp and hardwood bleached kraft pulp, and the product is made soft. can do.
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
- Medicinal Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Pest Control & Pesticides (AREA)
- Organic Chemistry (AREA)
- Oncology (AREA)
- Communicable Diseases (AREA)
- Dispersion Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
- Paper (AREA)
- Absorbent Articles And Supports Therefor (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06713958A EP1865106B1 (en) | 2005-03-30 | 2006-02-17 | Deodorant and antibacterial fiber product |
KR1020077022043A KR101223872B1 (ko) | 2005-03-30 | 2006-02-17 | 소취 항균 섬유제품 |
US11/886,906 US20090047363A1 (en) | 2005-03-30 | 2006-02-17 | Deodorant Antibacterial Fibrous Product |
CN2006800080368A CN101137789B (zh) | 2005-03-30 | 2006-02-17 | 除臭抗菌纤维制品 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005-100001 | 2005-03-30 | ||
JP2005100001 | 2005-03-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006112128A1 true WO2006112128A1 (ja) | 2006-10-26 |
Family
ID=37114870
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2006/302817 WO2006112128A1 (ja) | 2005-03-30 | 2006-02-17 | 消臭抗菌繊維製品 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20090047363A1 (ja) |
EP (1) | EP1865106B1 (ja) |
KR (1) | KR101223872B1 (ja) |
CN (1) | CN101137789B (ja) |
TW (1) | TWI443245B (ja) |
WO (1) | WO2006112128A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006307404A (ja) * | 2005-03-30 | 2006-11-09 | Kao Corp | 消臭抗菌繊維製品 |
JP2009011760A (ja) * | 2007-07-12 | 2009-01-22 | Soft99 Corporation | 芳香消臭器 |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102009029194A1 (de) * | 2009-09-04 | 2011-04-07 | Kimberly-Clark Worldwide, Inc., Neenah | Abtrennung gefärbter Stoffe aus wasserhaltigen Flüssigkeiten |
CN101947331A (zh) * | 2010-09-03 | 2011-01-19 | 云南清逸堂实业有限公司 | 一种卫生巾包合剂 |
CN102242531B (zh) * | 2011-05-27 | 2012-08-22 | 沈阳思特雷斯纸业有限责任公司 | 含天然矿粉的防腐杀菌纸及制造方法 |
US9220646B2 (en) | 2012-03-30 | 2015-12-29 | Kimberly-Clark Worldwide, Inc. | Absorbent articles with improved stain decolorization |
CN102720090A (zh) * | 2012-05-09 | 2012-10-10 | 连恩平 | 一种卫生纸的加工工艺 |
CN103564979A (zh) * | 2013-07-22 | 2014-02-12 | 常松 | 除臭调湿硅藻土鞋垫 |
KR101575314B1 (ko) * | 2014-03-18 | 2015-12-07 | 현대자동차 주식회사 | 차량용 알루미늄 휠 및 그 제조 방법 |
CN103981588B (zh) * | 2014-06-09 | 2016-01-13 | 青岛嘉胜隆贸易有限公司 | 一种抗菌除臭纤维素纤维及其制备方法 |
WO2016031749A1 (ja) * | 2014-08-29 | 2016-03-03 | 日本製紙株式会社 | 衛生薄葉紙、及びそれを用いた吸収性物品 |
KR102116907B1 (ko) * | 2015-07-22 | 2020-05-29 | 닛폰세이시가부시키가이샤 | 금속이온 함유 셀룰로오스 섬유, 이를 이용한 위생 박엽지 및 흡수성 물품 |
CN105239457A (zh) * | 2015-09-07 | 2016-01-13 | 龚灿锋 | 一种印刷纸张防霉干燥抗菌处理剂 |
JP6776103B2 (ja) * | 2016-11-22 | 2020-10-28 | 花王株式会社 | 消臭紙の製造方法 |
CN109730459B (zh) * | 2018-12-30 | 2020-11-13 | 台州宏玺工业设计有限公司 | 一种防臭鞋柜 |
EP3954826B1 (en) * | 2019-04-08 | 2024-01-17 | Kao Corporation | Antibacterial paper and method for manufacturing same |
CN113914135B (zh) * | 2021-11-05 | 2023-02-03 | 临沂三禾生物质科技有限公司 | 一种可完全降解的一次性鞋垫专用纸及其制备方法 |
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- 2006-02-17 US US11/886,906 patent/US20090047363A1/en not_active Abandoned
- 2006-02-17 WO PCT/JP2006/302817 patent/WO2006112128A1/ja active Application Filing
- 2006-02-17 KR KR1020077022043A patent/KR101223872B1/ko active IP Right Grant
- 2006-02-17 EP EP06713958A patent/EP1865106B1/en not_active Expired - Fee Related
- 2006-02-23 TW TW095106147A patent/TWI443245B/zh not_active IP Right Cessation
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JP2009011760A (ja) * | 2007-07-12 | 2009-01-22 | Soft99 Corporation | 芳香消臭器 |
Also Published As
Publication number | Publication date |
---|---|
TWI443245B (zh) | 2014-07-01 |
EP1865106B1 (en) | 2011-06-08 |
EP1865106A4 (en) | 2009-06-10 |
KR101223872B1 (ko) | 2013-01-17 |
TW200724749A (en) | 2007-07-01 |
EP1865106A1 (en) | 2007-12-12 |
CN101137789A (zh) | 2008-03-05 |
CN101137789B (zh) | 2012-09-05 |
KR20070114302A (ko) | 2007-11-30 |
US20090047363A1 (en) | 2009-02-19 |
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