JP2021123840A - Anti-allergen textile product - Google Patents

Abstract

To provide an improved anti-allergen product.SOLUTION: The present disclosure provides an anti-allergen product that has a composite fiber of hydrotalcite containing copper or zinc and a fiber. The composite fiber in the anti-allergen product has a fiber surface, 15% or more of which is coated with hydrotalcite.SELECTED DRAWING: Figure 2

Description

The present invention relates to an anti-allergen product containing a composite fiber of hydrotalcite and fiber.

In general, hydrotalcite has the general formula [M ²⁺ _1-x M ³⁺ _x (OH) ₂ ] [An ^- _{x / n} · mH ₂ O] (in the formula, M ²⁺ is a divalent metal ion, M. ³⁺ represents a trivalent metal ^{ion, a} _{n- x / n} is the representative of the interlayer anions. the 0 <x <1, n is represented by valence of a, is 0 ≦ m <1) It is one of the compounds used as a catalyst, a pharmaceutical, an additive for a resin, and the like (Patent Documents 1 to 3 and Non-Patent Document 1).

Hydrotalcite is a metal hydroxide having a layered crystal structure similar to talcite and smectite, and each crystal piece of hydrotalcite is often leaf-like or scaly. Hydrotalcite includes manasseite, which is a polytype of hydrotalcite, pyroaurite and sjgrenite, which contain magnesium and iron as metals in the hydroxide sheet, and divalent and trivalent iron in the hydroxide sheet. Known as green rust. Since the main skeleton is double hydroxide, it is also called layered double hydroxide (LDH). Hydrotalcite is naturally produced, but the amount produced is small, so synthetic products are mainly used, and various synthetic methods are known.

Patent Document 4 proposes a deodorant cloth in which a metal hydroxide such as hydrotalcite is supported on a polyurethane fiber or the like, and Patent Document 5 describes a method of fixing hydrotalcite to the fiber. Have been described. Further, Non-Patent Document 2 proposes to remove phosphorus from wastewater by using hydrotalcite-supporting fibers.

Japanese Unexamined Patent Publication No. 2015-193000 Japanese Unexamined Patent Publication No. 2013-085568 JP-A-2009-143798 Japanese Unexamined Patent Publication No. 2012-144829 International release WO2018 / 03521

"Application of Hydrotalcite to Water Environment Conservation and Purification", The Chemical Times, no. 1, 2005 "Phosphorus Removal Performance of Hydrotalcite-Supported Fiber (HTCF) from Actual Wastewater", Journal of Water Environment Society, vol. 30, no. 11, pp 671-676, 2007

An object of the present invention is to provide a textile product having excellent anti-allergen properties.

The present invention includes, but is not limited to, the following inventions.
[1] An anti-allergen product containing hydrotalcite containing copper and / or zinc and a composite fiber of a fiber, wherein 15% or more of the fiber surface is coated with hydrotalcite.

[2] The product according to [1], wherein the fiber is a chemical fiber, a regenerated fiber or a natural fiber. [3] The product according to [1] or [2], wherein the fiber is a cellulose fiber.
[4] The product according to any one of [1] to [3], wherein the trivalent metal ion of the hydrotalcite is aluminum.
[5] The product according to any one of [1] to [4], wherein the hydrotalcite contains hydrotalcite containing copper and zinc.

[6] The product according to any one of [1] to [5], which is in the form of a sheet or granules.
[7] The product according to any one of [1] to [6], wherein the allergen is Japanese cedar pollen or mites.
[8] The product according to any one of [1] to [7], wherein the deactivation removal rate for allergens is 70% or more.

Based on the present invention, a fiber product having excellent anti-allergenicity can be obtained by using a composite fiber of a hydrotalcite compound containing copper or zinc and a fiber. The anti-allergen product according to the present invention is suitable as a sanitary material such as a mask and a wiper sheet, and an adsorption material such as various filters.

It is a schematic diagram of the synthesis apparatus used in Example 1 (P: pump). It is an electron micrograph (3000 times) of the surface of the composite fiber of Example 1. It is an electron micrograph (3000 times) of the surface of the composite fiber of Example 2.

Hydrotalcite (HT)
In general, hydrotalcite is [M ²⁺ _1-x M ³⁺ _x (OH) ₂ ] [An ^- _{x / n} · mH ₂ O] (in the formula, M ²⁺ is a divalent metal ion, and M ³⁺ is. It represents a trivalent metal ^{ion, a} _{n- x / n} is. the 0 <x <1 represents an interlayer anion, n represents the general formula of the valence of a, is 0 ≦ m <1) Is done. ^{Here, M 2+} , which is a divalent metal ion, is a trivalent metal ion such as Mg ²⁺ , Co ²⁺ , Ni ²⁺ , Zn ²⁺ , Fe ²⁺ , Ca ²⁺ , Ba ²⁺ , Cu ²⁺ , and Mn ^2+. there ^{M 3+} are, for ^{example, Al 3+, Fe 3+, Cr} 3+, Ga 3+ , etc., which ^{a n-} is an interlayer anion, for _{^{example, OH -, Cl -, CO}} 3 -, SO 4 - n-valent such as Anions can be mentioned, where x is generally in the range 0.2-0.33. Of these, as the divalent metal ion, Mg ²⁺ , Zn ²⁺ , Fe ²⁺ , and Mn ²⁺ are preferable. The crystal structure has a laminated structure consisting of a two-dimensional basic layer in which brucite units of a regular octahedron having a positive charge are lined up and an intermediate layer having a negative charge.

Hydrotalcite has been used for various applications utilizing its anion exchange function, for example, for ion exchange materials, adsorbents, deodorants, and the like. In addition, by making the best use of the combination of the constituent metal ions and heating and dehydrating the hydrotalite in which each constituent metal ion is in a good mixed state, or by further heating and calcining, a composite oxide having a uniform composition can be easily obtained. In some cases, it is obtained in Japan and used for catalyst applications.

Synthesis of Hydrotalcite-Fiber Composite Fiber In the present invention, hydrotalcite-fiber composite fiber composite fiber is produced by synthesizing hydrotalcite in a solution in the presence of fiber.

The ratio of hydrotalcite in the composite fiber of the present invention can be 10% or more, 20% or more, and preferably 40% or more. The ash content of the composite fiber of hydrotalcite and fiber can be measured according to JIS P 8251: 2003. In the present invention, the ash content of the composite fiber of hydrotalcite and the fiber can be 10% or more, 20% or more, and preferably 40% or more. Further, the composite fiber of the hydrotalcite and the fiber of the present invention preferably contains magnesium, iron, manganese or zinc in an ash content of 10% or more, and more preferably 40% or more. The content of magnesium or zinc in the ash can be quantified by X-ray fluorescence analysis.

The present invention relates to a composite fiber of hydrotalcite and fiber, but in a preferred embodiment, 15% or more of the fiber surface is coated with hydrotalcite. In a preferred embodiment, the composite fiber of the present invention has a fiber coverage (area ratio) of hydrotalcite of 25% or more, more preferably 40% or more, but according to the present invention, the coverage is 60% or more. It is also possible to produce 70% or more, 80% or more of composite fibers. Further, in the composite fiber of hydrotalcite and fiber according to the present invention, in a preferred embodiment, it is possible that hydrotalcite is not only fixed on the outer surface of the fiber or inside the lumen, but also generated on the inside of the microfibril. It is clear from the results of microscopic observation.

The composite fiber with the inorganic particles is preferably used in an amount such that 15% or more of the fiber surface is covered with the inorganic particles. For example, the weight ratio of the fiber to the inorganic particles is 5/95 to 95/5. It may be 10/90 to 90/10, 20/80 to 80/20, 30/70 to 70/30, 40/60 to 60/40.

When hydrotalcite and fibers are made into composite fibers according to the present invention, not only is hydrotalcite easier to yield to the product, but also hydrotalcite is uniformly dispersed without agglomeration, as compared with the case where hydrotalcite is simply mixed with fibers. You can get the product. That is, according to the present invention, the yield of the composite fiber of hydrotalcite and fiber to the product (the weight ratio of the charged hydrotalcite remaining in the product) can be 65% or more, and 70% or more. Or 85% or more.

The method for synthesizing hydrotalcite can be a known method. For example, the fibers are immersed in a carbonate aqueous solution containing carbonate ions constituting an intermediate layer and an alkaline solution (sodium hydroxide, etc.) in a reaction vessel, and then an acid solution (divalent metal ions and trivalent metal ions constituting the basic layer) is immersed. Hydrotalite is synthesized by a co-precipitation reaction by adding a metal salt aqueous solution containing metal ions) and controlling the temperature, pH, etc. Further, in the reaction vessel, the fibers are immersed in an acid solution (a metal salt aqueous solution containing divalent metal ions and trivalent metal ions constituting the basic layer), and then a carbonate aqueous solution containing carbonate ions constituting the intermediate layer. It is also possible to synthesize hydrotalcite by a co-precipitation reaction by dropping an alkaline solution (sodium hydroxide or the like) and controlling the temperature, pH, etc. Although the reaction at normal pressure is common, there is also a method of obtaining it by a hydrothermal reaction using an autoclave or the like (Japanese Patent Laid-Open No. 60-6619).

In the present invention, various chlorides, sulfides, glass oxides, and sulfates of magnesium, zinc, barium, calcium, iron, copper, cobalt, nickel, and manganese are used as sources of divalent metal ions constituting the basic layer. Can be used. It is preferable to use a substance containing both zinc and copper as a source of divalent metal ions constituting the basic layer because it has a particularly excellent anti-allergen effect. Further, as a source of trivalent metal ions constituting the basic layer, various chlorides, sulfides, glass oxides and sulfates of aluminum, iron, chromium and gallium can be used.

In the present invention, water is used for preparing a suspension, and as this water, ordinary tap water, industrial water, groundwater, well water, etc. can be used, as well as ion-exchanged water, distilled water, and ultrapure water. Pure water, industrial wastewater, and water obtained during the manufacturing process can be preferably used.

In the present invention, carbonate ion, nitrate ion, chloride ion, sulfate ion, phosphate ion and the like can be used as the interlayer anion. When carbonate ions are used as interlayer anions, sodium carbonate is used as a source. However, sodium carbonate can be replaced with a gas containing carbon dioxide (carbon dioxide gas), and may be a substantially pure carbon dioxide gas or a mixture with other gases. For example, exhaust gas emitted from an incinerator, a coal boiler, a heavy oil boiler, or the like in a paper mill can be suitably used as a carbon dioxide-containing gas. In addition, a carbonation reaction can be carried out using carbon dioxide generated from the lime firing step.

When producing the composite fiber of the present invention, various known auxiliaries can be further added. For example, a chelating agent can be added to the neutralization reaction, specifically polyhydroxycarboxylic acids such as citric acid, malic acid and tartaric acid, dicarboxylic acids such as oxalic acid, sugar acids such as gluconic acid and iminoni. Amino polycarboxylic acids such as acetic acid and ethylenediamine tetraacetic acid and their alkali metal salts, alkali metal salts of polyphosphates such as hexametaphosphate and tripolyphosphate, amino acids such as glutamic acid and aspartic acid and their alkali metal salts, acetylacetone and acetoacetic acid. Examples thereof include ketones such as methyl and allyl acetoacetate, sugars such as sucrose, and polyols such as sorbitol. In addition, as a surface treatment agent, saturated fatty acids such as palmitic acid and stearic acid, unsaturated fatty acids such as oleic acid and linoleic acid, resin acids such as alicyclic carboxylic acid and avietic acid, salts and esters thereof and ethers and alcohols are used. Activators, sorbitan fatty acid esters, amide and amine surfactants, polyoxyalkylene alkyl ethers, polyoxyethylene nonylphenyl ethers, sodium alphaolefin sulfonate, long chain alkyl amino acids, amine oxides, alkylamines, fourth Primary ammonium salts, aminocarboxylic acids, phosphonic acids, polyvalent carboxylic acids, condensed phosphoric acids and the like can be added. Further, a dispersant can also be used if necessary. Examples of the dispersant include sodium polyacrylate, sucrose fatty acid ester, glycerin fatty acid ester, acrylic acid-maleic acid copolymer ammonium salt, methacrylic acid-naphthoxypolyethylene glycol acrylate copolymer, and methacrylic acid-polyethylene glycol. There are monomethacrylate copolymer ammonium salt, polyethylene glycol monoacrylate and the like. These can be used alone or in combination of two or more. The timing of addition may be before or after the neutralization reaction. Such additives can be added in an amount of preferably 0.001 to 20%, more preferably 0.1 to 10%, based on hydrotalcite.

(Reaction condition)
In the present invention, the temperature of the synthesis reaction can be, for example, 30 to 100 ° C., preferably 40 to 80 ° C., more preferably 50 to 70 ° C., and particularly preferably about 60 ° C. If the temperature is too high or too low, the reaction efficiency tends to decrease and the cost tends to increase.

Further, in the present invention, the neutralization reaction can be a batch reaction or a continuous reaction. In general, it is preferable to carry out the batch reaction step because of the convenience of discharging the residue after the neutralization reaction. The scale of the reaction is not particularly limited, but the reaction may be carried out on a scale of 100 L or less, or may be reacted on a scale of more than 100 L. The size of the reaction vessel may be, for example, about 10 L to 100 L, or about 100 L to 1000 L.

Furthermore, the neutralization reaction can be controlled by monitoring the pH of the reaction suspension, reaching, for example, less than pH 9, preferably less than pH 8, more preferably around pH 7, depending on the pH profile of the reaction solution. The carbonation reaction can be carried out until

On the other hand, the neutralization reaction can be controlled by monitoring the conductivity of the reaction solution. It is preferable to carry out the carbonation reaction until the conductivity decreases to 100 mS / cm or less.
Furthermore, the synthetic reaction can be controlled by the reaction time, and specifically, the time during which the reaction product stays in the reaction vessel can be adjusted and controlled. In addition, in the present invention, the reaction can be controlled by stirring the reaction solution in the reaction vessel or by making the neutralization reaction a multi-step reaction.

In the present invention, since the composite fiber which is a reaction product is obtained as a suspension, it is stored in a storage tank and subjected to treatments such as concentration, dehydration, pulverization, classification, aging and dispersion as necessary. Can be done. These can be performed by a known process, and may be appropriately determined in consideration of the application, energy efficiency, and the like. For example, the concentration / dehydration treatment is performed using a centrifugal dehydrator, a sedimentation concentrator, or the like. Examples of this centrifugal dehydrator include a decanter, a screw decanter, and the like. There is no particular limitation on the type of filter or dehydrator, and general ones can be used. For example, a pressurized dehydrator such as a filter press, a drum filter, a belt press, or a tube press can be used. A vacuum drum dehydrator such as an Oliver filter can be preferably used to prepare a calcium carbonate cake. As a crushing method, a ball mill, a sand grinder mill, an impact mill, a high pressure homogenizer, a low pressure homogenizer, a dyno mill, an ultrasonic mill, a kanda grinder, an attritor, a stone mill, a vibration mill, a cutter mill, a jet mill, a breaker, and a beating machine. , Short-screw extruder, twin-screw extruder, ultrasonic stirrer, household juicer mixer and the like. Examples of the classification method include a sieve such as a mesh, an outward type or inward type slit or round hole screen, a vibration screen, a heavy foreign matter cleaner, a lightweight foreign matter cleaner, a reverse cleaner, and a sieving tester. Examples of the dispersion method include a high-speed disperser and a low-speed kneader.

The composite fiber obtained by the present invention can be blended with a filler or a pigment in a suspension state without being completely dehydrated, or can be dried into a powder. The dryer in this case is also not particularly limited, but for example, an air flow dryer, a band dryer, a spray dryer, or the like can be preferably used.

By treating the composite fiber obtained by the invention with a weak acid such as dilute hydrochloric acid or dilute nitric acid, it is possible to intercalate chloride ions, nitrate ions and the like as interlayer ions. Examples of the compound to be intercalated include anionic substances, and examples thereof include a thiosulfato complex of copper or silver. As a method of intercalation, a known method can be used, but a solution containing an anionic substance can be added to the composite fiber of hydrotalcite and the fiber and mixed.

Further, the composite fiber obtained by the present invention can be modified by a known method. For example, in some embodiments, the surface can be made hydrophobic to improve miscibility with a resin or the like.

Fiber In the present invention, hydrotalcite and fiber are made into a composite fiber. The fibers that make up the composite fiber are not particularly limited, but for example, natural fibers such as cellulose, synthetic fibers artificially synthesized from raw materials such as petroleum, and regenerated fibers (semi-synthetic fibers) such as rayon and lyocell. ), Furthermore, inorganic fibers such as ceramics can be used without limitation. In addition to the above, natural fibers include protein fibers such as wool, silk thread and collagen fibers, and composite sugar chain fibers such as chitin / chitosan fibers and alginic acid fibers.

Examples of the cellulosic raw material include pulp fibers (wood pulp and non-wood pulp) and bacterial cellulose, and wood pulp may be produced by pulping the wood raw material. Wood raw materials include red pine, black pine, fir, spruce, beni pine, karamatsu, fir, tsuga, sugi, hinoki, karamatsu, shirabe, touhi, hiba, douglas fur, hemlock, white fur, spruce, balsam fur, cedar, pine, Coniferous trees such as Merck pine and Radiata pine, and their mixed materials, beech, hippo, hannoki, nara, tab, shii, white hippo, Hakoyanagi, poplar, fir, doroyanagi, eucalyptus, mangrove, lauan, acacia and other broad-leaved trees and their mixture. The material is exemplified.

The method for pulping a wood raw material is not particularly limited, and a pulping method generally used in the paper industry is exemplified. Wood pulp can be classified by the pulping method, for example, chemical pulp that has been vaporized by methods such as the craft method, sulfite method, soda method, and polysulfide method; mechanical pulp obtained by pulping with mechanical force such as a refiner and grinder; chemicals. Examples thereof include semi-chemical pulp; used paper pulp; and deinked pulp obtained by pulping by mechanical force after pretreatment with. The wood pulp may be in an unbleached (before bleaching) state or in a bleached (after bleaching) state.

Examples of non-wood-derived raw materials include cotton, hemp, sisal hemp, Manila hemp, flax, straw, bamboo, bagasse, kenaf, sugar cane, corn, rice straw, kozo, and mitsumata.

The pulp fiber may be unbeaten or beaten, and may be selected according to the physical characteristics of the composite fiber sheet, but beating is preferable. This can be expected to improve the sheet strength and promote the fixation of calcium carbonate.

Examples of synthetic fibers include polyester, polyamide, polyolefin, acrylic, nylon, acrylic, vinylon, and ceramic fibers, examples of semi-synthetic fibers include rayon and acetate, and examples of inorganic fibers include glass fibers, carbon fibers, and various metal fibers. Can be mentioned.

Further, these cellulose raw materials are further treated to carry out powdered cellulose, chemically modified cellulose such as oxidized cellulose, and cellulose nanofibers: CNF (microfibrillated cellulose: MFC, TEMPO oxide CNF, phosphoric acid esterified CNF, carboxymethylation). It can also be used as CNF, machine crushed CNF, etc.). The powdered cellulose used in the present invention has a constant particle size having a rod-like shape, which is produced by, for example, a method of purifying and drying an undecomposed residue obtained after acid hydrolysis of selected pulp, crushing and sieving. Crystalline cellulose powder having a distribution may be used, or commercially available products such as KC Flock (manufactured by Nippon Paper Industries), Theoras (manufactured by Asahi Kasei Chemicals), and Abyssel (manufactured by FMC) may be used. The degree of polymerization of cellulose in powdered cellulose is preferably about 100 to 1500, the degree of crystallinity of powdered cellulose by X-ray diffraction is preferably 70 to 90%, and the volume average particle diameter by a laser diffraction type particle size distribution measuring device. Is preferably 1 μm or more and 100 μm or less. The cellulose oxide used in the present invention can be obtained by oxidizing in water with an oxidizing agent in the presence of, for example, an N-oxyl compound and a compound selected from the group consisting of bromide, iodide or a mixture thereof. can. As the cellulose nanofiber, the method of defibrating the above-mentioned cellulose raw material is used. As a defibration method, for example, an aqueous suspension of chemically modified cellulose such as cellulose or oxidized cellulose is mechanically ground or beaten with a refiner, a high-pressure homogenizer, a grinder, a uniaxial or multiaxial kneader, a bead mill or the like. This makes it possible to use a method of defibrating. Cellulose nanofibers may be produced by combining one or more of the above methods. The fiber diameter of the produced cellulose nanofibers can be confirmed by observation with an electron microscope or the like, and is, for example, in the range of 5 nm to 1000 nm, preferably 5 nm to 500 nm, and more preferably 5 nm to 300 nm. When producing the cellulose nanofibers, before and / or after the cellulose is defibrated and / or finely divided, an arbitrary compound may be further added and reacted with the cellulose nanofibers to modify the hydroxyl groups. can. Functional groups to be modified include acetyl group, ester group, ether group, ketone group, formyl group, benzoyl group, acetal, hemiacetal, oxime, isonitrile, allene, thiol group, urea group, cyano group, nitro group and azo group. , Aryl group, aralkyl group, amino group, amide group, imide group, acryloyl group, methacryloyl group, propionyl group, propioloyl group, butyryl group, 2-butyryl group, pentanoyl group, hexanoyl group, heptanoil group, octanoyl group, nonanoyl group. , Decanoyl group, undecanoyl group, dodecanoyl group, myritoyl group, palmitoyl group, stearoyl group, pivaloyl group, benzoyl group, naphthoyl group, nicotinoyyl group, isonicotinoyl group, floyl group, cinnamoyl group and other acyl groups, 2-methacryloyloxyethyl isothia Isocyanate group such as noyl group, methyl group, ethyl group, propyl group, 2-propyl group, butyl group, 2-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl Examples thereof include an alkyl group such as a group, an undecyl group, a dodecyl group, a myristyl group, a palmityl group and a stearyl group, an oxylan group, an oxetane group, an oxyl group, a thiirane group and a thietan group. Hydrogen in these substituents may be substituted with a functional group such as a hydroxyl group or a carboxyl group. Further, a part of the alkyl group may have an unsaturated bond. The compound used for introducing these functional groups is not particularly limited, and for example, a compound having a phosphoric acid-derived group, a compound having a carboxylic acid-derived group, a compound having a sulfuric acid-derived group, and a sulfonic acid-derived compound. Examples thereof include a compound having a group of, a compound having an alkyl group, a compound having a group derived from amine, and the like. The compound having a phosphoric acid group is not particularly limited, and examples thereof include phosphoric acid, lithium dihydrogen phosphate which is a lithium salt of phosphoric acid, dilithium hydrogen phosphate, trilithium phosphate, lithium pyrophosphate, and lithium polyphosphate. .. Further, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate, sodium polyphosphate, which are sodium salts of phosphoric acid, can be mentioned. Further, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, potassium pyrophosphate, potassium polyphosphate, which are potassium salts of phosphoric acid, can be mentioned. Further, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, ammonium polyphosphate and the like, which are ammonium salts of phosphoric acid, can be mentioned. Of these, phosphoric acid, a sodium salt of phosphoric acid, a potassium salt of phosphoric acid, and an ammonium salt of phosphoric acid are preferable from the viewpoint of high efficiency of introducing a phosphoric acid group and easy industrial application, and sodium dihydrogen phosphate. , Monosodium hydrogen phosphate is more preferable, but it is not particularly limited. The compound having a carboxyl group is not particularly limited, and examples thereof include dicarboxylic acid compounds such as maleic acid, succinic acid, phthalic acid, fumaric acid, glutaric acid, adipic acid and itaconic acid, and tricarboxylic acid compounds such as citric acid and aconitic acid. .. The acid anhydride of the compound having a carboxyl group is not particularly limited, and examples thereof include acid anhydrides of dicarboxylic acid compounds such as maleic anhydride, succinic anhydride, phthalic anhydride, glutaric anhydride, adipic anhydride, and itaconic anhydride. Be done. The derivative of the compound having a carboxyl group is not particularly limited, and examples thereof include an imide product of an acid anhydride of a compound having a carboxyl group and a derivative of an acid anhydride of a compound having a carboxyl group. The imide of the acid anhydride of the compound having a carboxyl group is not particularly limited, and examples thereof include an imide of a dicarboxylic acid compound such as maleimide, succinateimide, and phthalateimide. The derivative of the acid anhydride of the compound having a carboxyl group is not particularly limited. For example, at least a part of hydrogen atoms of the acid anhydride of a compound having a carboxyl group, such as dimethylmaleic anhydride, diethylmaleic anhydride, diphenylmaleic anhydride, etc., are substituents (for example, alkyl group, phenyl group, etc.). ) Replaced by). Among the compounds having a group derived from the carboxylic acid, maleic anhydride, succinic anhydride, and phthalic anhydride are preferable because they are easily applied industrially and easily gasified, but are not particularly limited. Further, the cellulose nanofibers may be modified in such a manner that the modifying compound is physically adsorbed on the cellulose nanofibers without being chemically bonded. Examples of the compound that is physically adsorbed include a surfactant and the like, and any of anionic, cationic and nonionic compounds may be used. If the above modification is performed before defibration and / or pulverization of cellulose, these functional groups can be eliminated after defibration and / or pulverization to return to the original hydroxyl group. By applying the above modifications, it is possible to promote the defibration of the cellulose nanofibers and to facilitate mixing with various substances when the cellulose nanofibers are used.

The fibers shown above may be used alone or in combination of two or more. Among them, it is preferable to contain wood pulp or a combination of wood pulp and non-wood pulp and / or synthetic fiber, and more preferably only wood pulp.

In a preferred embodiment, the fibers constituting the composite fiber of the present invention are pulp fibers. Further, for example, a fibrous substance recovered from wastewater from a paper mill may be used in the present invention. By supplying such a substance to the reaction vessel, various composite particles can be synthesized, and fibrous particles and the like can be synthesized in terms of shape.

The fiber length of the composited fiber is not particularly limited, but for example, the average fiber length can be about 0.1 μm to 15 mm, and may be 10 μm to 12 mm, 50 μm to 10 mm, 200 μm to 8 mm, or the like. Of these, in the present invention, it is preferable that the average fiber length is longer than 50 μm because dehydration and sheet formation are easy. It is more preferable that the average fiber length is longer than 1 mm because dehydration and sheeting can be performed by using a wire (filter) mesh for dehydration and / or papermaking used in a normal papermaking process.
The fiber diameter of the fiber to be composited is not particularly limited, but for example, the average fiber diameter can be about 1 nm to 100 μm, 10 nm to 100 μm, 0.15 μm to 100 μm, 1 μm to 90 μm, 3 to 50 μm, 5 to 30 μm. And so on. Of these, in the present invention, it is preferable that the average fiber diameter is higher than 500 nm because water and sheet formation are easy. It is more preferable that the average fiber diameter is larger than 20 μm because dehydration and sheeting can be performed by using a wire (filter) mesh for dehydration and / or papermaking used in a normal papermaking process.

Allergen substance An allergen substance is a substance that can be a cause of allergy, and examples thereof include an antigen that specifically reacts with an antibody of a person having an allergic disease. Typical allergen substances include pollen (cedar, hinoki, etc.) that causes pollinosis, perennial allergic rhinitis, bronchial asthma, mites and indoor dust (house dust) that cause atopic dermatitis. ..

The product of the present invention has high anti-allergen properties, and the deactivation removal rate for allergen substances may be 50% or more, preferably 70% or more, and further 80% or more. The deactivation removal rate (%) can be calculated from the following formula.
"Inactivation removal rate (%)" = [1- (residual amount of allergen in test sample) / (residual amount of allergen in control sample)] x 100
Molded product of composite fiber It is also possible to appropriately manufacture a molded product (body) using the composite fiber according to the present invention. For example, when the composite fiber obtained by the present invention is made into a sheet, a sheet having a high ash content can be easily obtained. Examples of the paper machine (paper machine) used for sheet production include a long net paper machine, a round net paper machine, a gap former, a hybrid former, a multi-layer paper machine, and a known paper machine that combines the paper making methods of these devices. Be done. The press line pressure in the paper machine and the calendar line pressure when the calendar processing is performed in the subsequent stage can be set within a range that does not affect the operability and the performance of the composite fiber sheet. Further, starch, various polymers, pigments and mixtures thereof may be applied to the formed sheet by impregnation or coating.

Wet and / or dry paper strength agents (paper strength enhancers) can be added during sheeting. Thereby, the strength of the composite fiber sheet can be improved. Examples of paper strength agents include urea formaldehyde resin, melamine formaldehyde resin, polyamide, polyamine, epichlorohydrin resin, vegetable gum, latex, polyethyleneimine, glyoxal, gum, mannogalactan polyethyleneimine, polyacrylamide resin, and polyvinylamine. , Polyvinyl alcohol and the like; composite polymers or copolymer polymers composed of two or more kinds selected from the above resins; starches and processed starches; carboxymethyl cellulose, guar gum, urea resins and the like. The amount of the paper strength agent added is not particularly limited.

In addition, a high molecular polymer or an inorganic substance can be added in order to promote the fixation of the filler to the fiber and to improve the yield of the filler and the fiber. For example, as a coagulant, polyethyleneimine and modified polyethyleneimine containing a tertiary and / or quaternary ammonium group, polyalkyleneimine, dicyandiamide polymer, polyamine, polyamine / epiclohydrin polymer, and dialkyldialyl quaternary ammonium monomer, dialkyl. Aminoalkyl acrylates, dialkylaminoalkylmethacrylates, dialkylaminoalkylacrylamides, dialkylaminoalkylmethacrylate and acrylamide polymers, polymers consisting of monoamines and epihalohydrins, polymers with polyvinylamine and vinylamine moieties, and cations such as mixtures thereof. In addition to the sex polymer, a cation-rich amphoteric polymer in which an anionic group such as a carboxyl group or a sulfone group is copolymerized in the molecule of the polymer, or a mixture of a cationic polymer and an anionic or amphoteric polymer is used. be able to. Further, as the retention agent, a cationic or anionic or amphoteric polyacrylamide-based substance can be used. In addition to these, a yield system called a so-called dual polymer, in which at least one or more cation or anionic polymers are used in combination, can be applied, and at least one or more anionic bentonite, colloidal silica, polysilicic acid, etc. can be applied. It is a multi-component yield system that uses one or more of inorganic fine particles such as polysilicic acid or polysilicate microgels and their aluminum modified products, and organic fine particles with a particle size of 100 μm or less, which are so-called micropolymers cross-linked and polymerized with acrylamide. May be good. In particular, when the polyacrylamide-based substance used alone or in combination has a weight average molecular weight of 2 million daltons or more by the ultimate viscosity method, a good yield can be obtained, preferably 5 million daltons or more, more preferably. Can obtain a very high yield when it is the above-mentioned acrylamide-based substance of 10 million daltons or more and less than 30 million daltons. The form of this polyacrylamide-based substance may be an emulsion type or a solution type. The specific composition is not particularly limited as long as the substance contains an acrylamide monomer unit as a structural unit, and is, for example, a copolymer of a quaternary ammonium salt of an acrylic acid ester and acrylamide, or acrylamide. Acrylic acid ester is copolymerized with and then quaternized ammonium salt. The cationic charge density of the cationic polyacrylamide-based substance is not particularly limited.

In addition, depending on the purpose, inorganic particles such as drainage improver, internal sizing agent, pH adjuster, defoamer, pitch control agent, slime control agent, bulking agent, calcium carbonate, kaolin, talc, silica, etc. (so-called) Filling fee) and the like. The amount of each additive used is not particularly limited.

It is also possible to use a molding method other than sheeting. For example, a method called pulp molding in which a raw material is poured into a mold for suction dehydration and drying, or a method of spreading and drying on the surface of a molded product such as resin or metal is used. After that, molded products having various shapes can be obtained by a method of peeling from the base material or the like. Further, it can be molded into a plastic by mixing a resin, or it can be molded into a ceramic by adding a mineral such as silica or alumina and firing it. In the compounding / drying / molding shown above, only one type of composite fiber may be used, or two or more types of composite fibers may be mixed and used. When two or more kinds of composite fibers are used, those which are mixed in advance can be used, or those which are mixed, dried and molded by each can be mixed later.

When producing a molded product (body) using the composite fiber according to the present invention, various organic substances such as polymers, various inorganic substances such as pigments, and various fibers such as pulp fibers may be added. Further, various organic substances such as polymers, various inorganic substances such as pigments, and various fibers such as pulp fibers may be added to the molded product of the composite fiber later.

The composite fibers obtained by the present invention can be used for various purposes, for example, paper, fibers, cellulose-based composite materials, filter materials, paints, plastics and other resins, rubbers, elastomers, ceramics, glass, tires. , Building materials (asphalt, asbestos, cement, boards, concrete, bricks, tiles, plywood, fiberboard, etc.), various carriers (catalyst carriers, pharmaceutical carriers, pesticide carriers, microbial carriers, etc.), excipients (purification of impurities, deodorization, etc.) , Dehumidification, etc.), anti-wrinkle agent, clay, abrasive, modifier, repair material, heat insulating material, moisture-proof material, water-repellent material, water-resistant material, light-shielding material, sealant, shield material, insect repellent, adhesive, ink, Cosmetics, medical materials, paste materials, food additives, tablet excipients, dispersants, shape-retaining agents, water-retaining agents, filtration aids, essential oil materials, oil treatment agents, oil modifiers, radio wave absorbers, insulating materials , Sound insulation material, anti-vibration material, semiconductor encapsulant material, radiation blocking material, cosmetics, fertilizer, feed, fragrance, paint / adhesive / resin additive, discoloration inhibitor, conductive material, heat transfer material, sanitary goods (disposable) It can be widely used for all purposes such as diapers, sanitary napkins, incontinence pads, breast milk pads). Further, it can be used as various fillers, coating agents and the like in the above-mentioned applications. Of these, adsorbents (impurity removal, deodorization, dehumidification, etc.) and hygiene products (disposable diapers, sanitary napkins, incontinence pads, breast milk pads) are preferable.

The composite fiber of the present invention may be applied to papermaking applications, for example, printing paper, newspaper, inkjet paper, PPC paper, kraft paper, high-quality paper, coated paper, finely coated paper, wrapping paper, thin leaf paper, and high-quality color. Paper, cast-coated paper, non-carbon paper, label paper, heat-sensitive paper, various fancy papers, water-soluble paper, release paper, process paper, wallpaper base paper, non-combustible paper, flame-retardant paper, laminated board base paper, printed electronics paper, battery Separator, cushion paper, tracing paper, impregnated paper, ODP paper, building material paper, decorative paper, envelope paper, tape paper, heat exchange paper, synthetic fiber paper, sterilized paper, water resistant paper, oil resistant paper, heat resistant paper, photocatalyst Paper, decorative paper (greasy paper, etc.), various sanitary papers (toilet paper, tissue paper, wipers, diapers, sanitary goods, etc.), tobacco paper, paperboard (liner, core base paper, white paperboard, etc.), paper plate base paper, cups Examples include base paper, baking paper, abrasive paper, and synthetic paper.

Hereinafter, the present invention will be described in more detail with reference to specific experimental examples, but the present invention is not limited to the following experimental examples. Further, unless otherwise specified in the present specification, the concentration, parts, etc. are based on weight, and the numerical range is described as including the end points thereof.

1. 1. Preparation of sample The following aqueous solution was prepared in order to synthesize a copper-zinc-based or zinc-based hydrotalcite compound (HT).

1-1. Example 1 (Sample 1, FIG. 2)
Copper-zinc-based hydrotalcite compound was prepared _{(CuZn 5 Al 2 (OH)} 16 CO 3 · 4H 2 O) and the composite fiber sheet of pulp fibers.

Cellulose fiber was used as the fiber to be composited. Specifically, it contains broad-leaved bleached kraft pulp (LBKP, manufactured by Nippon Paper Industries) and softwood bleached kraft pulp (NBKP, manufactured by Nippon Paper Industries) in a weight ratio of 8: 2, and uses a single disc refiner (SDR) to perform Canadian standard drainage. Pulp fibers adjusted in degree to 390 ml were used.

Pulp fibers were added to an alkaline solution to prepare an aqueous suspension containing the pulp fibers (pulp fiber concentration: 3.5%, pH: 12.9). This aqueous suspension (pulp solid content 100 g) is placed in a 10 L reaction vessel, and while stirring the aqueous suspension, solution B (mixed acid solution of three types of reagents) is added dropwise as an acid solution to hydrotal. A composite fiber of site fine particles and fiber was synthesized. Using an apparatus as shown in FIG. 1, the reaction temperature was 50 ° C., the dropping rate was 5 to 15 ml / min, and dropping was stopped when the pH of the reaction solution reached about 7. After completion of the dropping, the reaction solution was stirred for 30 minutes and washed with 10 times the amount of water to remove the salt.

Then, an aqueous suspension having a concentration of 0.5 to 1.0% was prepared from the obtained composite fiber, and a hand paper ^{having a basis weight of 100 g / m 2 was prepared using a 150 mesh wire according to JIS P 8222: 1998.} A mesh sheet was prepared (basis weight: about 100 g / m ² ).

1-2. Example 2 (Sample 2, FIG. 3)
To produce a composite fiber sheet of the zinc-based hydrotalcite compound _{(Zn 6 Al 2 (OH)} 16 CO 3 · 4H 2 O) and the pulp fibers.

A sheet was produced by synthesizing a composite fiber of hydrotalcite fine particles and fibers in the same manner as in Example 1 except that C solution (mixed acid solution of two kinds of reagents) was used as the acid solution.
1-3. Example 3 (Sample 3)
Processing the composite fibers of Example 2 with copper sulfate solution, the composite fibers of the zinc-based hydrotalcite carrying copper _{(Zn 6 Al 2 (OH)} 16 CO 3 · 4H 2 O and Cu, composite fibers with the pulp fibers ) Was obtained. Specifically, copper sulfate pentahydrate was dissolved in water to prepare a copper sulfate solution having a concentration of 5%. This copper sulfate solution was added to the slurry (concentration 3.5% by weight) of Sample 2 before washing so that the weight% concentration of copper per solid content was 2.0%, and the temperature was 50 ° C. Stirred. After completion of the dropping, the reaction solution was stirred for 30 minutes and washed with 10 times the amount of water to remove the salt. Then, the sheet was manufactured by the same method as in Example 1.

1-4. Example 4 (Sample 4)
To produce a composite fiber sheet of the copper-based hydrotalcite compound _{(Cu 6 Al 2 (OH)} 16 CO 3 · 4H 2 O) and the pulp fibers. A sheet was produced by synthesizing a composite fiber of hydrotalcite fine particles and fibers in the same manner as in Example 1 except that the D solution (mixed acid solution of two kinds of reagents) was used as the acid solution.

1-5. Example 5 (Sample 5, non-woven fabric sheet)
A non-woven fabric sheet containing the composite fiber of Example 1 was produced. The copper-zinc hydrotalcite composite fiber produced in Example 1 and a binder fiber (heat-fused fiber) were mixed in a composition of 60:40 to obtain a raw material for a wet non-woven fabric. As the binder fiber (heat fusion fiber), a core-sheath type polyester composite fiber (melting point of the sheath portion: 100 to 160 ° C., core portion: polyethylene terephthalate) was used. Further, in order to improve the wet strength, 0.3% by weight of a polyamide epoxy-based wet paper strength agent was added, and then the raw material was dispersed in water. Then, using this raw material, a sheet was produced in the same manner as in Example 1.

1-6. Example 6 (Sample 6, Granules)
Granules were produced using the composite fiber of Example 3 as a raw material. Specifically, a copper-supported zinc-based hydrotalcite composite fiber (moisture content: about 70%) was put into a Proshare mixer (WB type, Pacific Machinery & Engineering Co., Ltd.) and stirred at room temperature. Subsequently, steam was poured into the Proshare mixer to raise the temperature inside the apparatus to 80 ° C. or higher, and the mixture was dried while stirring. After drying until the water content reached about 10%, granulation was performed while adding water (finished particle size after granulation: about 0.5 mm, water content after granulation: about 50%). Finally, using a 0.5 mesh sieve, granules having a particle size of 0.5 mm or less were obtained.

1-7. Comparative Example 1 (Sample 7)
To produce a composite fiber sheet of the magnesium-based hydrotalcite compound _{(Mg 6 Al 2 (OH)} 16 CO 3 · 4H 2 O) and the pulp fibers.

A sheet was produced by synthesizing a composite fiber of hydrotalcite fine particles and fibers in the same manner as in Example 1 except that E solution (mixed acid solution of two kinds of reagents) was used as the acid solution.
1-8. Comparative Example 2 (Sample 8)
To produce a composite fiber sheet of rutile titanium oxide supported magnesium-based hydrotalcite compound _{(Ti + Mg 6 Al 2 (} OH) 16 CO 3 · 4H 2 O) and the pulp fibers.

A sheet was produced by synthesizing a composite fiber of hydrotalcite fine particles and fibers in the same manner as in Comparative Example 1 except that rutile-type titanium oxide (manufactured by Sakai Chemical Co., Ltd.) was added to the alkaline solution.
1-9. Comparative Example 3 (Sample 9)
To produce a composite fiber sheet of anatase type titanium oxide supported magnesium-based hydrotalcite compound _{(Ti + Mg 6 Al 2 (} OH) 16 CO 3 · 4H 2 O) and the pulp fibers.

A sheet was produced by synthesizing a composite fiber of hydrotalcite fine particles and fibers in the same manner as in Comparative Example 1 except that anatase-type titanium oxide (manufactured by Sakai Chemical Co., Ltd.) was added to the alkaline solution in addition to the pulp fibers. ..

1-10. Comparative Example 4 (Sample 10: Non-woven fabric sheet)
A sheet was produced in the same manner as in Example 5 except that the dissociated copper-zinc hydrotalcite composite fiber was not added.

1-11. Comparative Example 5 (Sample 11: Pulp Sheet)
Contains bleached broadleaf kraft pulp (LBKP, manufactured by Nippon Paper Industries) and bleached softwood kraft pulp (NBKP, manufactured by Nippon Paper Industries) in a weight ratio of 8: 2, and adjusts the Canadian standard drainage to 390 ml using a single disc refiner (SDR). A sheet was produced in the same manner as in Example 1 using the resulting pulp fibers.

1-12. Comparative Example 6 (Sample 12)
The zinc-based hydrotalcite alone was produced by the same method as in Example 2 except that pulp was not added. An aqueous suspension having a concentration of 0.5 to 1.0% was prepared at a ratio of 70% by mass of the pulp prepared in Comparative Example 5 and 30% by mass of the produced zinc-based hydrotalcite, and the same as in Example 1. The sheet was manufactured by the method.

1-13. Comparative Example 7 (Sample 13)
The simple substance of copper-based hydrotalcite was produced by the same method as in Example 4 except that pulp was not added. An aqueous suspension having a concentration of 0.5 to 1.0% was prepared at a ratio of 70% by mass of the pulp prepared in Comparative Example 5 and 30% by mass of the produced copper-based hydrotalcite, and the same as in Example 1. The matte sheet was manufactured by the method.

1-14. Example 7 (Sample 14)
A composite fiber of magnesium-based hydrotalcite compound fine particles and fibers was synthesized in the same manner as in Example 1 except that E solution (mixed acid solution of two kinds of reagents) was used as the acid solution. Then, processes the composite fibers in the same manner as in Example 3 with copper sulfate solution, copper magnesium was supported based hydrotalcite compound _{(Mg 6 Al 2 (OH)} 16 CO 3 · 4H 2 O) and the pulp fibers A composite fiber sheet was manufactured.

1-15. Example 8 (Sample 15, non-woven fabric sheet)
A non-woven fabric sheet containing the composite fibers of Example 1 was produced in the same manner as in Example 5 except that a retention agent was added. Specifically, a cationic retention agent (ND300, Hymo) was added at 100 ppm with respect to solid content, and then the raw material was dispersed in water, which was used as the raw material for the wet non-woven fabric.

2. Sample evaluation 2-1. Observation with an electron microscope An electron microscope (SEM) was used to observe the obtained composite fibers, and it was confirmed that the particles were composited on the surface of the pulp fibers.

1 and 2 are electron micrographs (3000 times) of the surfaces of the composite fibers of Example 1 and Example 2, respectively. In the composite fiber, the coverage of the pulp fiber with the fine particles was 50 to 80% (primary particle size of the fine particles: 100 to 900 nm, average primary particle size: about 400 nm).

2-2. Weight ratio of inorganic particles The weight ratio of inorganic particles was calculated based on the ash content. The ash content of the composite fiber was calculated from the ratio of the weight of the remaining ash to the original solid content after heating the composite fiber at 525 ° C. for about 2 hours (JIS P 8251: 2003). However, since the ashing treatment at 525 ° C. causes a weight loss due to decarboxylation of hydrotalcites and desorption of interlayer water, the inorganic content contained in the composite fiber is taken into consideration from the measured weight after the ashing treatment. The weight ratio of the particles was calculated.

The weight ratio of Cu or Zn was obtained by quantifying Cu or Zn contained in ash heated at 525 ° C. for about 2 hours using an energy dispersive fluorescent X-ray analyzer (EDX-7000, manufactured by Shimadzu Corporation). The weight (%) of Cu or Zn contained in the composite fiber was calculated from the quantitative value and the ash content.

2-3. Anti-allergen characteristics The anti-allergen characteristics were evaluated using the manufactured sample sheet (basis weight: about 100 g / m ^2).

The anti-allergen properties were evaluated by the deactivation-removing effect of Japanese cedar pollen allergen (Cry j1) and mite allergen (Der f2), and tested by an external testing institute.
Dissolve purified Cry j1 (manufactured by Biochemical Biobusiness) or purified rDer f2 (manufactured by Asahi Food & Healthcare) at 100 ng / mL in phosphate buffered saline (PBS) containing 0.05% tween 20. Then, a test solution was prepared. Under room temperature conditions, 0.2 g of the sample was placed in a 15 ml plastic tube and 1 ml of the test solution was brought into contact with the sample. After standing for 1 hour, the sample was squeezed with a finger to extract the test solution, centrifuged at 10000 × g for 3 minutes, and the allergen concentration (Cry j1 concentration or rDer f2 concentration) in the supernatant was measured by the sandwich ELISA method. As a comparative control, only the test solution was measured.

The allergen concentration (Cry j1 concentration or rDer f2 concentration) was measured by the sandwich ELISA method under the following conditions.
・ N = 2 (2 well) per sample
-Measuring equipment: MULTISKAN FC (Thermo)
-Measurement wavelength: 405 nm
The deactivation removal rate (%) was calculated from the following formula. The deactivation removal rate was calculated using sample 11 (pulp sheet) as a control, but only for sample 5, the deactivation removal rate was calculated using sample 10 (nonwoven fabric) as a control.
"Inactivation removal rate (%)" = [1- (residual amount of allergen in test sample) / (residual amount of allergen in control sample)] x 100
2-4. Yield Calculated as a percentage of the value obtained by dividing the absolute dry weight of the obtained sample by the absolute dry weight of the added raw material, and evaluated according to the following criteria.
・ ○: 90% or more ・ ×: Less than 90%

As is clear from the results shown in the table, it was found that the sheet of the present invention has a high anti-allergen effect. In particular, it was found that Sample 1 containing both copper and zinc had an excellent anti-allergen effect, and that the non-woven fabric of Sample 5 also had an anti-allergen effect of 75% or more. On the other hand, in Samples 7 to 11 of Comparative Examples, the anti-allergen effect could not be confirmed. It is speculated that the presence of copper or zinc contributed to the development of anti-allergen effects. Further, since the yields of the samples 12 and 13 of the comparative example are poor, it is not possible to efficiently obtain a textile product.

Claims (8)

An anti-allergen product containing a composite fiber of hydrotalcite containing copper and / or zinc and a fiber, wherein 15% or more of the fiber surface is coated with hydrotalcite. The product according to claim 1, wherein the fiber is a chemical fiber, a regenerated fiber or a natural fiber. The product according to claim 1 or 2, wherein the fiber is a cellulose fiber. The product according to any one of claims 1 to 3, wherein the trivalent metal ion of the hydrotalcite is aluminum. The product according to any one of claims 1 to 4, wherein the hydrotalcite contains hydrotalcite containing copper and zinc. The product according to any one of claims 1 to 5, which is in the form of a sheet or granules. The product according to any one of claims 1 to 6, wherein the allergen is Japanese cedar pollen or mites. The product according to any one of claims 1 to 7, wherein the deactivation removal rate for allergens is 70% or more.

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