JP2007075131A - Deodorant material and deodorant sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a deodorant material and a deodorant sheet, excellent in the deodorization capability, to be stably held inside various base material sheets. <P>SOLUTION: The deodorant material is characterized by the micro-gel resin with anionic and/or cationic groups. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a deodorizing material and a deodorizing sheet. More specifically, the present invention is useful as a powdery deodorizing agent and imparts a deodorizing property to a base sheet such as various synthetic fibers, synthetic resins and paper. The present invention relates to a useful deodorizing material. Furthermore, it is a deodorizing material that is effective for imparting deodorizing properties to base sheets such as diapers, sanitary products, sweat-absorbing materials, and fibers and paper used in homes. The present invention relates to a deodorizing material and a deodorizing sheet having excellent permeability and air permeability.

  Conventionally, in the fields of wallpaper, decorative boards, building materials, fibers, non-woven fabrics, clothing, various films, etc., these products themselves are often required to have malodor removal, so-called deodorization, and various deodorizing materials (agents). Has been used.

  In the field of liquid-absorbing sanitary deodorizing sheets such as paper diapers and sanitary products, many studies have been made to add deodorizing functions to various products, and the development of products with effective deodorizing functions has continued. (See Patent Documents 1 and 2, etc.). In Patent Documents 3 and 4, for example, there are many studies on compounding a powdery deodorant such as zeolite or activated carbon with a water-absorbing base sheet. Since the deodorization function greatly depends on factors such as type, composition, and combination method, the selection of these factors is an important issue during product development.

As for the deodorizing agent, it is known to use a deodorizing agent composed of a resin having an ion-exchange group. However, these deodorizing agents have large particles and a small reaction area with malodorous components, so the deodorizing effect is There was a limit. In addition, a physical adsorption type deodorant represented by activated carbon has a problem in that it has a large adsorption area, but has a low ability to adsorb malodorous components and low practical performance. In recent years, there is an increasing demand for higher performance for these deodorizers, and in particular, there is a strong demand for improved deodorization performance.
Japanese Patent No. 2862274 JP 2000-350745 A JP-A 63-23366 JP-A-62-211068

  Accordingly, an object of the present invention is to provide a deodorizing material and a deodorizing sheet that are excellent in deodorizing ability and are stably held inside or on the surface of various substrate sheets.

The above object is achieved by the present invention below.
That is, the present invention provides a deodorizing material comprising a microgel resin having an anionic and / or cationic group (hereinafter referred to as “microgel”). In the deodorizing material, the average particle size of the microgel is 0.01 μm to 100 μm; the anionic group of the microgel is at least one selected from a sulfone group, a sulfate ester group, a phosphate ester group, and a carboxyl group The cationic group of the microgel is preferably at least one selected from a quaternary pyridinium group, a quaternary ammonium group, and a primary to tertiary amino group.

  Moreover, this invention provides the deodorizing sheet characterized by including the said microgel in the base-material surface or a base material. In the deodorizing sheet, the content of the microgel resin is 0.6 to 100 parts by mass per 100 parts by mass of the substrate sheet; the substrate is cellulose paper, woven fabric or nonwoven fabric; and the nonwoven fabric However, it is preferable that it is a sulfonated polypropylene nonwoven fabric.

  Further, the present invention provides a method for producing a deodorizing sheet in which the microgel dispersed in a dispersion medium is supported on a fibrous base sheet by a paper making method, and a base sheet by applying the microgel dispersion to the base sheet. Provided is a method for producing a deodorizing sheet to be carried on a substrate. In these methods, a water absorbent resin powder can be further mixed.

  As a result of intensive studies to solve the above problems, the present inventors have dispersed the microgel having the ionic group in a liquid medium and applied it to various substrate sheets or mixed the substrate. It has been found that a deodorizing sheet can be obtained which can be combined with the sheet and can effectively remove malodorous substances such as ammonia and mercaptans.

  Since the microgel used in the present invention is a microsphere (average particle size: 0.01 to 100 μm), it has a large surface area, and when the ionic group is a cationic group, it produces a cationic malodor, such as ammonia, When the functional group is an anionic group, malodors such as anionic mercaptans can be effectively removed.

  In addition, by dispersing the microgel in an aqueous medium together with a binder resin, it is suitable for preparing a base paper for decorative board, a deodorizing woven fabric, a raw material for wallpaper, etc. without contaminating the spraying place. be able to. Further, by forming a layer made of the above-mentioned microgel on the base sheet, contamination of other deodorizing sheets due to ammonia ions eluted from the deodorizing material is prevented, and air permeability and water permeability are maintained. Furthermore, this microgel provides an excellent deodorizing effect when used in disposable diapers and sanitary napkins.

Next, the present invention will be described in more detail with reference to preferred embodiments.
The microgel that characterizes the present invention is one in which polymer fine particles are internally crosslinked and has an anionic group and / or a cationic group. As a typical method for producing the microgel as described above, there is a method of radical polymerization of a mixture of a monomer and a crosslinkable monomer as described later in either an aqueous or non-aqueous system. Examples of the polymerization method include soap-free polymerization, suspension polymerization, dispersion polymerization, and seed polymerization. From the viewpoint of the polymerization mechanism, the emulsion polymerization method, the soap-free polymerization method and the seed polymerization method are preferable because the particle diameter of the microgel can be reduced. In particular, a surfactant may be used as an emulsifier during polymerization, but soap-free polymerization using an amphiphilic monomer is preferred because there is no contamination of the active agent.

  Representative monomers for preparing the microgel include, for example, styrene, methyl acrylate, (meth) acrylic acid (or their salts), maleic acid, methyl maleate, styrene sulfone groups (or their salts), (Meth) acryloyloxypropylsulfone group (or salt thereof), sulfopropyl (meth) acrylate (or salt thereof), 2-sulfoethyl (meth) acrylate (or salt thereof), 2- (meth) Acryloylamino-2-methyl-1-propanesulfone group (or salt thereof), 2- (meth) acryloylamino-2-propanesulfone group (or salt thereof), vinylsulfone group (or salt thereof), 4 -Vinyl pyridine, 2-vinyl pyridine, N, N-dimethylaminoethyl acrylate, N, N Such as dimethylaminopropyl acrylamide.

  Examples of the crosslinkable monomer that is copolymerized with the above monomer and internally crosslinks the resulting resin include divinylbenzene, methylenebis (meth) acrylamide, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and others 3 To 4-functional (meth) acrylates. In particular, divinylbenzene is preferred for preparing a microgel in an aqueous system. When these crosslinkable monomers are used, the crosslinkable monomer is used in an amount of 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the monomer constituting the polymer. To do.

  Other copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, hydroxyethyl (meth) acrylate, (meth) acrylic acid Polyethylene glycol (meth) acrylate hydroxypropyl, (meth) acrylic acid ester derivatives such as polypropylene glycol (meth) acrylate, (meth) acrylamide, N-methyl (meth) acrylamide, N-methylol (meth) acrylamide, N- Examples include (meth) acrylamide derivatives such as butoxymethyl (meth) acrylamide and N, N-dimethylacrylamide, acrylonitrile, vinyl acetate and the like.

  The microgel used in the present invention is a crosslinked sphere polymer having a diameter in the range of 0.01 to 100 μm, preferably in the range of 0.02 to 5 μm. When the diameter of the microgel is less than 0.01 μm, it is difficult to form pores in the microgel. On the other hand, when the diameter of the microgel exceeds 100 μm, the microgel settles when dispersed in the dispersion medium and applied. Therefore, the microgel application process becomes complicated.

  The microgel used in the present invention is classified into an anionic microgel and a cationic microgel, and the anionic microgel is an anionic group such as a sulfone group, a carboxyl group, a sulfate ester group or a phosphate ester group, preferably a sulfone group or a carboxyl group. Has a group. On the other hand, the cationic microgel has a cationic group such as a primary to tertiary amino group, a quaternary ammonium group, or a quaternary pyridinium group. In addition, after producing a non-ionic microgel, an ionic microgel may be produced by chemical modification treatment such as amination and quaternary ammoniumation, hydrolysis, sulfonation, and sulfate esterification.

  A microgel having a sulfonic group can be obtained by preparing a fine particle of a polystyrene-divinylbenzene copolymer having a diameter of about 200 nm by various methods known in the art, such as a soap-free polymerization method, followed by drying and sulfonation. . The sulfonation amount at this time is adjusted by selecting the sulfonation conditions in a sulfonation method, for example, a method using concentrated sulfuric acid or a mixture of concentrated sulfuric acid and fuming sulfuric acid, or a method of sulfonating the fine particles with sulfur trioxide gas. it can.

  As a typical example of a microgel having a carboxyl group, there is a method disclosed in Japanese Patent Application Laid-Open No. 2003-178797. If this method is used, a large amount of carboxyl groups can be introduced into the microgel, which is preferable. To restate, hydrophobic methyl acrylate and cross-linking agent divinylbenzene are polymerized using sodium styrene sulfonate in an aqueous system, and after polymerization, the methyl ester group is hydrolyzed to form a carboxyl group salt, followed by It can be acidified to introduce carboxyl groups into the microgel. According to this method, a sulfone group can be introduced into the microgel surface and a large amount of carboxyl groups can be introduced into the microgel.

  As a typical microgel having a cationic group, for example, a microgel obtained by quaternizing 4-vinylpyridine or copolymer fine particles of 2-vinylpyridine and divinylbenzene can be given. 4-Vinylpyridine or 2-vinylpyridine is an amphiphilic monomer, and when this monomer is copolymerized with a water-soluble polymerization initiator, fine particles of 200 to 600 nm are formed. Next, the obtained fine particles are dispersed in methyl alcohol, methyl iodide is added to the dispersion, and salt exchange is performed with hydrochloric acid or excess NaCl, KCl, etc. to obtain a cationic microgel having a particle size of about 360 nm. Can do.

  The amount of ionic groups introduced into the microgel having styrene units is in the range of 0.01 to 1.1 substitutions per styrene unit when the ionic group is a sulfone group. Preferably it is the range of 0.5-1.0 piece. If the number of sulfone groups is less than 0.01, the deodorizing effect of the resulting microgel is small, while it is difficult to introduce more than 1.1 sulfone groups.

  When the ionic group is a carboxyl group, it is in the range of 15 to 99.5 mol% in terms of acrylic acid unit. When the carboxyl group is less than 15 mol%, the deodorizing effect of the resulting microgel is small, while the carboxyl group is If it exceeds 99.5 mol%, the cross-linked structure is small, the strength of the resulting microgel is weak, and the microgel may break during handling of the microgel.

  In the case of a vinylpyridine microgel having a cationic group, it is in the range of 15 to 99.5 mol% in terms of pyridine unit, and if the quaternary pyridinium group is less than 15 mol%, the deodorizing effect of the resulting microgel is small, When the quaternary pyridinium group exceeds 99.5 mol%, the cross-linked structure is small, the strength of the resulting microgel is weak, and the microgel may be broken during handling of the microgel.

  As the polymerization initiator used in the above polymerization, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2-azobis (2-methylpropinoamidino) dihydrochloride, 2,2′- Water-soluble polymerization initiators such as azobis (2-amidinopropane) diacetate, 2,2'-azobis (N, N'-dimethyleneisobutylamidine) dihydrochloride, ammonium persulfate, potassium persulfate, '-Azobisisobutyronitrile, 2,2'-azobis (methylisobutyrate), 2,2'-azobis (2,4-dimethylvaleronitrile), 1,1'-azobis (cyclohexane-1-carbohydrate) Nitrile), cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, lauryl peroxide, etc. And the like.

  The deodorizing sheet of the present invention is characterized by containing the microgel as described above on the surface of the base sheet or inside the base sheet. Examples of the base sheet used here include water-permeable paper, synthetic paper, woven fabric, and non-woven fabric. Particularly, in the present invention, when water-permeable paper is used, malodorous components such as ammonia and mercaptan are used. A deodorizing sheet excellent in deodorizing is provided.

A preferable method for uniformly containing the microgel as described above on or in the base sheet is a method of making paper by mixing the microgel as described above with (1) an aqueous dispersion of cellulosic fibers (internal addition formula). ,
(2) There is a method of dispersing the microgel in water or an organic solvent, and applying and drying the dispersion on the surface of the base sheet. In the above internal formula, paper is made by mixing an aqueous dispersion of microgel and an aqueous dispersion of cellulose fibers such as pulp, or paper is made by adding and mixing microgel in powder or paste form to an aqueous dispersion of cellulose fibers. .

  Various additives can be added to the paper internally or coated with the microgel of the present invention as necessary, and examples of the additive include a viscosity modifier, a dispersion stabilizer, and a pigment.

  The fiber used in the present invention may be any fiber that can be easily dispersed uniformly in water. For example, natural fibers represented by cellulose fibers, inorganic fibers such as glass fibers and rock wool, polyvinyl alcohol fibers, nylon fibers, polyester fibers, polypropylene fibers, polyacrylonitrile fibers, aromatic polyamide fibers such as Kevlar, ceramic fibers, etc. Synthetic fibers can be used alone or in combination. Cellulose fibers are particularly preferred, and more specifically, cellulose fibers such as wood pulp, cotton fibers, cotton, plant pulp, and recovered waste paper. Although there is no restriction | limiting in particular about the length and diameter of a fiber, Usually, a length is about 0.5-100 mm and thickness is about 5-70 micrometers.

  In the paper internally added or coated with the microgel of the present invention, the content of the microgel with respect to 100 parts by mass of pulp is 0.6 to 100 parts by mass, preferably 1 to 40 parts by mass. When the content of the microgel is less than 0.6 parts by mass, the deodorizing property of the paper is insufficient. On the other hand, when the content of the microgel is larger than 100 parts by mass, the strength of the paper is not sufficient, the loss of the microgel at the time of papermaking is large, and the contamination of the papermaking drainage becomes severe. Since the microgel used in the present invention is excellent in dispersibility in an aqueous solvent and the strength of the obtained paper is large, it is possible to easily make paper without adding an auxiliary agent.

  Various auxiliary agents that are usually used can be used as needed during papermaking. For example, inorganic substances such as talc, diatomaceous earth, silica, titanium dioxide, barium sulfate, calcium carbonate, aluminum nitrate, magnesium carbonate, alum, aqueous dispersions of organic polymers, and antioxidants, carboxymethylcellulose, methylcellulose, etc. Cellulose derivatives, dyes, color pigments, starches, starch derivatives, waxes, acrylamide copolymers and their derivatives, melamine formaldehyde resins, urea aldehyde resins, crosslinkers such as epoxy compounds, various sizes such as polyethyleneimine, rosin, etc. Agents, cationic, anionic or nonionic surfactants can be used alone or in combination of two or more. These can be used as such or in the form of an aqueous dispersion or emulsion.

  The microgel dispersion used in the coating method is obtained by dispersing the microgel as described above alone or a composite of the microgel and the binder resin in water, a mixed medium of water and an organic solvent, or an organic medium alone. . Examples of the organic solvent used by mixing with water include methanol, ethanol, propanol, acetone, methyl ethyl ketone, ethylene glycol, diethylene glycol, acetates thereof or lower alcohol ethers, dioxane, pyrrolidone, dimethylformamide, formamide, dimethylsulfoxide, and the like. Is mentioned. Examples of the medium used alone as the organic solvent include cyclohexane, methyl ethyl ketone, and toluene. The solid content of the microgel in water and / or organic solvent is usually 1-10% by mass, preferably 3-5% by mass.

  As the binder resin used in the present invention, for example, acrylic resins, vinyl acetate resins, and other binder resins used in various conventional water-based paints and printing inks can be used. The addition concentration of the binder resin may be any, but is generally preferably about 10 to 50% by mass in the microgel dispersion. These binder resins may be dissolved in an aqueous medium, or may be dispersed or emulsified.

  As a method for dispersing the microgel in the aqueous medium, any of a ball mill, a speed line mill, a sand mill, a roll mill, a paint shaker and the like conventionally used in the pigment field can be used. The concentration of the microgel component of the dispersion is not particularly limited, but is generally preferably about 5 to 50% by mass.

  Further, when dispersing the microgel, it is preferable to use a dispersant or a surfactant. As the surfactant, a nonionic surfactant is used at a concentration of 0.5 to 10% by mass in the dispersion. Is preferably used. In the present invention, it is preferable to dissolve or disperse the above dispersion in a vehicle containing such a conventionally known binder resin so that the microgel has a concentration of about 10 to 30% by mass. In addition, a colorant such as a dye or a pigment can be added to the microgel dispersion of the present invention as described above.

  Furthermore, known additives such as extender pigments such as calcium carbonate and silica, white pigments such as titanium oxide, colorants, and antibacterial / antifungal agents can be added to the dispersion solution. For the formation of the microgel layer, a binder resin can be used as necessary in order to enhance the adhesion to the base sheet. When the binder resin is used in a large amount, the water permeability and air permeability to the microgel layer are lowered, so that it is 10 parts by mass or less, preferably 1 part by mass or less per 100 parts by mass of the microgel. As the binder resin used in the present invention, a hydrophobic or water-soluble resin can be used.

  Particularly preferred binder resins include, for example, water-soluble resins such as polyvinyl alcohol and polyethylene oxide. Examples of hydrophobic resins include polybutadiene rubber, polyisoprene, polyisobutylene, and butadiene-acrylonitrile copolymer. Rubber, styrene-butadiene copolymer rubber and hydrogenated products thereof, chloroprene rubber, nitrile rubber, raw rubber, urethane rubber, acrylic rubber, ethylene-vinyl acetate copolymer rubber, and chlorinated products thereof may be used alone or in a mixture. These copolymers can be used, and any type of bonding such as block type, random type, and graft type may be used.

Moreover, as a base material sheet used by this invention, the woven fabric, nonwoven fabric, or porous film which consists of a polypropylene-type or polyethylene-type fiber is preferable, for example. Furthermore, the said fiber can also be used. Basis weight of the woven or non-woven is preferably in the range of 10 to 300 g / m ^2. When the basis weight is less than 10 g / m ² , the microgel falls off, while when the basis weight exceeds 300 g / m ² , the microgel dispersion liquid hardly enters the base sheet. As for the thickness of the fiber which comprises the said nonwoven fabric or woven fabric, 1-10 micrometers is preferable.

  These substrate sheets may or may not be hydrophilized, but it is generally preferable to hydrophilize them. Examples of hydrophilization include sulfonation treatment, corona discharge treatment, a method of applying a resin solution having a carboxyl group or a hydroxyl group, and a method of partially weaving hydrophilic fibers in a woven or non-woven fabric. In particular, sulfonation is an effective treatment for increasing the ammonia deodorizing effect. The sulfonation treatment amount is a treatment amount at which the woven or non-woven fabric has 0.1 to 5% by mass of sulfone groups. If the amount of the sulfone group in the woven or non-woven fabric is less than 0.1% by mass, the hydrophilic property of the woven or non-woven fabric is weak, and the impregnation property of the microgel aqueous dispersion is insufficient. The detachment of the sulfone group from the cloth or non-woven fabric increases, and the strength of the woven or non-woven fabric decreases.

Examples of the coating method of the microgel dispersion on the substrate sheet surface include conventionally known methods such as roll coating, blade coating, knife coating, squeeze coating, air doctor coating, gravure coating, rod coating, spray coating, and impregnation. The coating method is mentioned, A microgel layer is formed by drying after coating. If the coating amount of such a microgel layer is too small, the anion or cation adsorptivity is insufficient. On the other hand, if the coating amount is too large, water permeability and air permeability are lowered and it is uneconomical, so a preferable coating amount is 1 to 80 g / m. It is about ² .

  Next, the present invention will be described more specifically with reference to examples and comparative examples. In the text, parts or percentages are based on mass.

〔Example〕
Production Example of Microgel (1) Production of Microgels 1 and 2 125 parts of styrene, 13.75 parts of sodium styrenesulfonate, 15.78 parts of divinylbenzene (pure 55%), 2.32 parts of potassium persulfate and water 1 And 500 parts were charged into a flask and polymerized at 80 ° C. for 8 hours under a nitrogen stream. The average particle diameter of the obtained polymer was about 100 nm. The granular polymer was filtered, dried and pulverized to obtain a white polymer. The particle size of the polymer fine particles obtained was 200 nm as measured by a dynamic light scattering method. Next, a microgel having a sulfone group was synthesized by the following two methods (gas method and sulfuric acid treatment method).

(Gas treatment method)
Sulfur dioxide gas produced by pre-drying 100 parts of powdered polystyrene (average particle size 0.020 μm) of (1) at 105 ° C. for 1 hour in a dryer, and placing it in a reaction vessel to burn sulfur. Sulfur trioxide gas obtained by catalytic oxidation was heated to 80 to 110 ° C. and introduced into the reaction vessel so as to have a concentration of 8% with respect to dry air, and sulfonated for 2 hours. Thereafter, the mixture was cooled and the sulfonated polystyrene was put into ion-exchanged water and stirred, and then filtered and washed with water until the pH became constant. Then, it dried at 80 degreeC for 24 hours, and the sulfonated polystyrene (microgel-1) was obtained. This microgel was confirmed to have almost one sulfone group introduced into the aromatic ring by analysis such as infrared absorption spectrum and ion chromatography. The sulfur content of the microgel was 10%, and the S / C ratio was 90.

(Sulfuric acid treatment method)
100 parts of the powdery polystyrene of (1) was gradually added to 650 parts of 95% concentrated sulfuric acid and stirred at 50 ° C. for 24 hours and then at 80 ° C. for 3 hours. Then, it cooled and thrown the reaction liquid mixture into a lot of ice water. Thereafter, the filtrate was peptized, filtered, washed with water until it became neutral, and washed thoroughly with water. Then, it dried at 80 degreeC for 24 hours, and the sulfonated polystyrene (microgel-2) was obtained. This microgel was confirmed to have almost one sulfone group introduced into the aromatic ring by analysis such as infrared absorption spectrum and ion chromatography. The microgel had a sulfur content of 10% and an S / C ratio of 85.

(2) Production of microgel-3 70 parts methyl acrylate, 3 parts sodium styrene sulfonate, 3.66 parts divinylbenzene (55% pure), 1.5 parts potassium persulfate and 550 parts deionized Water was put into a reaction vessel and polymerized at 80 ° C. for 6 hours under a nitrogen stream. The particle size of the copolymer in the polymerization solution was 300 to 500 nm as measured by a dynamic light scattering method. Next, a 10% aqueous potassium hydroxide solution was prepared, and the acrylate resin was added thereto, and reacted at 70 ° C. for 4 hours. Thereafter, 1.2 times mole of hydrochloric acid in terms of potassium acrylate was added and stirred at room temperature for 1 hour. Further, filtration, peptization and washing were carried out until the filtrate became neutral to obtain microgel-3 (carboxyl group-containing fine particles). The obtained microgel-3 confirmed that the ester group was converted into the carboxyl group by analysis, such as an infrared absorption spectrum and ion chromatography.

(3) Production of microgel-4 (4-vinylpyridinium-based fine particles) 500 parts deionized water, 10 parts 4-vinylpyridine, 0.1 parts divinylbenzene, 0.1 parts acrylamide and 0 in a reaction vessel .2 parts of 2,2-azobis (2-methylpropinoamidino) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries, Ltd.) was charged and polymerized at 80 ° C. for 5 hours under nitrogen gas flow to give an emulsion. Obtained. This was dialyzed using a cellulose dialysis membrane and purified with deionized water. As a result of observation with a scanning electron microscope, it was confirmed that the particles were homogeneous spherical fine particles having an average particle diameter of 200 nm. Furthermore, this particle | grain was put into the sealed container containing methyl iodide and methanol, and the spherical fine particle and the vinyl pyridine in a continuous phase were quaternized, and the microgel-4 was obtained.

(4) Production example of deodorizing sheet (internal addition method)
The deodorization sheet was prepared (internal addition method) by a method of making a microgel on paper. Specifically, the microgel of the example is added to a predetermined amount of the pulp dispersion aqueous solution with stirring, and a flocculant and a neutralizing agent are sequentially added to obtain a raw liquid. Water was added to this stock solution, and an organic fixing agent (yield improving material) was further added to obtain a stock solution. This was hand-papered, the paper was peeled off from the wire mesh, press-compressed and dehydrated, and then air-dried to obtain the microgel-added paper of Example. The amount of microgel added was as shown in Tables 1 and 3. In addition, about microgel-1, the thing of addition amount 40% and 80% was also created.

(5) Production example of deodorizing sheet (application method)
5 parts of the microgel of the example was added to 100 parts of a mixed solvent having a mass ratio of water: IPA = 7/3, and dispersed by stirring for 1 hour to prepare a microgel dispersion, and 100 mm × 200 mm filter paper (No. 2 (manufactured by Toyo Roshi Kaisha, Ltd.)), a polypropylene nonwoven fabric and a sulfonated polypropylene nonwoven fabric, coated with a bar coater, then dried, and the microgel coated paper and the microgel coated nonwoven fabric of the coating amounts shown in Tables 2 and 4 Got.

[Comparative example]
As comparative examples of deodorizers, activated carbon for deodorization use, synthetic zeolite (molecular sieve), and paper deodorant were added or applied to pulp in the same manner as the above microgel, and the amount added was 20%. Each deodorized paper was made. The deodorized paper obtained in the above Examples and Comparative Examples was evaluated by the following evaluation methods.

[Deodorization performance measurement test method]
Ammonia deodorization test 1
3 μl of 4% aqueous ammonia solution was placed in a 300 ml Erlenmeyer flask, the mouth was sealed with parafilm, and completely gasified. After that, each deodorized paper is cut into 50 mm × 50 mm, put into the container and stored at 25 ° C., and the ammonia concentration in the flask after a certain time has passed is measured with the Kitagawa type gas detector. It was measured. The deodorizing property of each deodorizing sheet was as shown in Tables 1-2.

Ammonia deodorization test 2 (application method)
The deodorizing paper and nonwoven fabric were measured in the same manner as described above, and the results were as follows.

Deodorization test of hydrogen sulfide 1 ml of 700 ppm sodium sulfide aqueous solution and 0.1 ml of 1N sulfuric acid were placed in a 300 ml Erlenmeyer flask, then each of the deodorized paper or deodorized non-woven fabric was cut into 50 mm x 50 mm and put into the container. The mouth was sealed with parafilm to completely gasify the hydrogen sulfide. Then, it preserve | saved at 25 degreeC and the result of having measured the hydrogen sulfide in the flask after a fixed time progress with the Kitagawa type gas detector was as Tables 3 and 4 below.

  The microgel produced by the present invention and the sheet prepared therefrom can be used after being processed into a suitable form as a material for sanitary products, diapers and the like.

  The above-described microgel of the present invention can be used for a base paper for decorative board, a deodorizing woven fabric, and a wallpaper without contaminating a spraying place by dispersing a microgel alone or a composite of a microgel and a binder resin in an aqueous medium. It can be preferably used for the preparation of raw materials and the like, and it is effective for deodorizing ammonia odor and hydrogen sulfide odor in various malodors, and can be provided for sanitary and sanitary products such as diapers.

Claims (11)

  A deodorizing material comprising a microgel resin having an anionic and / or cationic group.   The deodorizing material according to claim 1, wherein the average particle size of the microgel resin is 0.01 µm to 100 µm.   The deodorizing material according to claim 1, wherein the anionic group of the microgel resin is at least one selected from a sulfone group, a sulfate ester group, a phosphate ester group, and a carboxyl group.   The deodorizing material according to claim 1, wherein the cationic group of the microgel resin is at least one selected from a quaternary pyridinium group, a quaternary ammonium group, and a primary to tertiary amino group.   A deodorizing sheet comprising a microgel resin having an anionic and / or cationic group on the substrate surface or in the substrate.   The deodorizing sheet according to claim 5, wherein the content ratio of the microgel resin is 0.6 to 100 parts by mass per 100 parts by mass of the base sheet.   The deodorizing sheet according to claim 6, wherein the substrate is cellulose paper, woven fabric, or non-woven fabric.   The deodorizing sheet according to claim 7, wherein the nonwoven fabric is a sulfonated polypropylene nonwoven fabric.   A method for producing a deodorizing sheet, comprising supporting a microgel resin having an anionic and / or cationic group dispersed in a dispersion medium in a fiber base sheet by a paper making method.   A method for producing a deodorizing sheet, wherein a dispersion liquid in which a microgel resin having an anionic and / or cationic group is dispersed in a dispersion medium is supported on a base sheet by a coating method.   Furthermore, the manufacturing method of the deodorizing sheet of Claim 9 or 10 which mixes a water absorbing resin powder.