JP2022156677A - Method for storing composite fibers of fibers and inorganic particles - Google Patents

Abstract

To provide a storage method that prevents the propagation of bacteria and mold, causing quality deterioration or malodors, even when complexes of fibers and inorganic particles are stored in a wet state.SOLUTION: A method for storing composite fibers includes the steps of: adding a fungicide and/or a preservative to a suspension of composite fibers of fibers and inorganic particles with a concentration of 0.01-7 mass%; and concentrating the suspension of composite fibers to 25 mass% or more in concentration.SELECTED DRAWING: None

Description

The present invention relates to a method for storing composite fibers of fibers and inorganic particles.

Cellulose fibers, including wood fibers, exhibit various properties based on the functional groups on their surface, and depending on the application, it may be necessary to modify the surface. Technologies have been developed to do so.

For example, fibers can exhibit various properties by attaching inorganic particles to their surfaces. Regarding the technique of precipitating inorganic particles on fibers such as cellulose fibers, Patent Document 1 discloses a technique of producing a composite fiber of pulp and calcium carbonate by precipitating calcium carbonate in a pulp suspension by a carbon dioxide gas method. is described (Patent Document 1).

U.S. Pat. No. 5,679,220

However, when stored in a wet state (solid content concentration of about 25 to 60% by mass), conjugated fibers of fibers and inorganic particles, especially conjugated fibers made from pulp, may generate mold and bacteria, resulting in deterioration of quality. was there. In addition, when the composite fiber is stored in a dry state (solid content concentration of 90% by mass or more) to prevent the generation of mold and bacteria, when the composite fiber is diluted with water and re-macerated, the coating with inorganic particles is removed from the fiber surface. There was a problem that more peeling occurred and the performance of the composite fiber deteriorated.

An object of the present invention is to provide a method for preventing the propagation of bacteria and fungi, which cause deterioration in quality and offensive odor, when a composite of fibers and inorganic particles is stored in a wet state.

The present inventors have made intensive studies to solve the above problems, and as a result, the step of adding an antifungal agent and / or an antiseptic to a composite fiber suspension having a concentration of 0.01 to 7% by mass, the composite Concentrating the fiber suspension to a concentration of 25% by mass or more by adjusting the concentration of the composite fiber can effectively reduce the growth of bacteria and mold. , have completed the present invention.

The present invention includes, but is not limited to, the following inventions.
(1) A method for storing composite fibers of fibers and inorganic particles, comprising a step of adding an antifungal agent and/or a preservative to a composite fiber suspension having a concentration of 0.01 to 7% by mass, the composite fiber suspension The above method, comprising a step of concentrating the liquid to a concentration of 25% by mass or more.
(2) The method according to (1), wherein the antifungal agent and/or antiseptic agent contains an isothiazolone compound.
(3) The method according to (1) or (2), wherein the antifungal agent and/or preservative is added to the composite fiber suspension in an amount of 1 to 10,000 mg/L.

According to the present invention, even when a composite of fibers and inorganic particles is stored in a wet state, it is possible to prevent the growth of bacteria and fungi that cause quality deterioration and offensive odors.

The present invention comprises a step of adding an antifungal agent and/or a preservative to a composite fiber suspension of inorganic particles and fibers at a concentration of 0.01 to 7% by mass, and increasing the concentration of the composite fiber suspension to 25. A step of concentrating to mass % or more is provided.

Antifungal agent and/or antiseptic agent The antifungal agent and/or antiseptic agent used in the present invention includes isothiazolone compounds (5-chromium-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazoline -3-one, methylenebisthiocyanate, 4,5-dichloro-2-n-octyl-isothiazolin-3-one, 2-n-octyl-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, etc. ), glyoxime compounds (dichloroglyoxime, etc.), bromcyano compounds (2,2-dibromo-3-nitrilopropionamide, 2-bromo-2-bromomethylglutaronitrile, etc.), halogenated nitro alcohol compounds (2, 2-dibromo-2-nitroethanol, 2-bromo-2-nitro-1,3-propanediol, etc.), bromonitro compounds (2-bromo-2-nitropropane-1,3-diol, 2,2-dibromo- 2-Nitro-1-ethanol, 2-bromo-2-nitro-1-ethanol, 1,1-dibromo-1-nitro-2-propanol, 1,1-dibromo-1-nitro-2-acetoxyethane, 1 ,1-dibromo-1-nitro-2-acetoxypropane, 2-bromo-2-nitro-1,3-diacetoxy-propane, tribromonitromethane, β-bromo-β-nitrostyrene, 5-bromo-5-nitro -1,3-dioxane, 5-bromo-2-methyl-5-nitro-1,3-dioxane, etc.), bromoacetic ester compounds (1,2-bis-(bromoacetoxy)-ethane, 1,2- bis(bromoacetoxy)-propane, 1,4-bis-(bromoacetoxy)-2-butene, methylenebisbromoacetate, benzyl bromoacetate, 1,2,3-tris(bromoacetoxy)propane, N-bromoacetamide, 2-bromoacetamide, etc.), organic sulfur compounds (3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide, bis(tribromomethyl)sulfone, bis(trichloromethyl)sulfone, etc.), be done. Among these, isothiazolone compounds are preferred.

The amount of the antiseptic and/or antifungal agent added is preferably 1 to 10000 mg/L, more preferably 100 to 5000 mg/L, particularly preferably 500 to 3000 mg/L, in the composite fiber suspension.

Concentration of composite fibers In the present invention, after the step of synthesizing inorganic particles in a solution containing fibers and producing composite fibers of inorganic particles and fibers, a composite fiber suspension having a concentration of 0.01 to 7% by mass is added. A step of concentrating to 25% by mass or more is provided. The concentration is preferably 25-50% by mass, more preferably 28-50% by mass, and particularly preferably 30-45% by mass. Concentration and dehydration of the composite fiber are performed using, for example, a centrifugal dehydrator, a sedimentation concentrator, or the like. Examples of this centrifugal dehydrator include decanters and screw decanters. When using a filter or dehydrator, there is no particular limitation on the type thereof, and common ones can be used. A vacuum drum dehydrator such as an Oliver filter can be suitably used. After concentrating the conjugate fiber to a concentration of 25% by mass or more, it may be stored in a flexible container bag or the like, or may be transported immediately. When the concentration of the conjugate fibers is less than 25% by mass, the residual ratio of the inorganic particle conjugate fibers after disaggregation decreases. Further, when the concentration of the conjugate fiber exceeds 50% by mass, the time required for disaggregation after transportation becomes long.

Synthesis of composite fibers In the present invention, composite fibers can be synthesized by synthesizing inorganic particles in a solution containing fibers such as cellulose fibers. This is because the fiber surface becomes a suitable place for precipitation of inorganic particles, and conjugate fibers are easily synthesized. As a method for synthesizing the conjugate fiber, for example, a solution containing precursors of fibers and inorganic particles may be stirred and mixed in an open reaction tank to synthesize conjugate fibers, or precursors of fibers and inorganic particles may be synthesized. may be synthesized by injecting an aqueous suspension containing into the reaction vessel. As will be described later, when injecting an aqueous suspension of an inorganic precursor into a reaction vessel, cavitation bubbles may be generated to synthesize inorganic particles in the presence of the bubbles. Each of the inorganic particles can be synthesized on the cellulose fibers by known reactions.

In general, the formation of inorganic particles proceeds from a cluster state (repeating aggregation and scattering at a stage where the number of atoms and molecules that are gathered is small) to a nucleus (cluster) to a stable aggregation state, and when it reaches a critical size or more, it is caught. atoms/molecules stop scattering) and growth (new atoms/molecules gather in the nucleus and the particles grow larger). is said to be easy. The conjugate fiber of the present invention can be produced by adjusting the raw material concentration, the beating degree (specific surface area) of the pulp, the viscosity of the solution containing the fiber, the concentration and addition speed of the additive chemical, the reaction temperature, and the stirring speed. By efficiently binding the nuclei and promoting particle growth, it is possible to obtain composite fibers in which the surfaces of the cellulose fibers are strongly coated with inorganic particles.

In the present invention, the liquid may be jetted under conditions that generate cavitation bubbles in the reaction vessel, or under conditions that do not generate cavitation bubbles. Also, the reaction vessel is preferably a pressure vessel in any case. In addition, the pressure vessel in the present invention means a vessel to which a pressure of 0.005 MPa or more can be applied. Under conditions that do not cause cavitation bubbles, the pressure in the pressure vessel is preferably 0.005 MPa or more and 0.9 MPa or less in terms of static pressure.

(Cavitation bubbles)
When synthesizing the composite fiber according to the present invention, inorganic particles can be precipitated in the presence of cavitation bubbles. In the present invention, cavitation is a physical phenomenon in which bubbles are generated and disappear in a short time due to a pressure difference in a fluid flow, and is also called a cavitation phenomenon. Bubbles caused by cavitation (cavitation bubbles) are generated with very small "bubble nuclei" of 100 microns or less existing in the liquid as nuclei when the pressure in the fluid becomes lower than the saturated vapor pressure for a very short time.

In the present invention, cavitation bubbles can be generated in the reaction vessel by a known method. For example, generating cavitation bubbles by injecting a fluid at high pressure, generating cavitation by agitating the fluid at high speed, generating cavitation by generating an explosion in the fluid, and ultrasonic vibration. It is conceivable that cavitation is generated by the child (vibratory cavitation).

In the present invention, cavitation can be generated by directly using the reaction solution such as the raw material as the injection liquid, or cavitation bubbles can be generated by injecting some fluid into the reaction vessel. The fluid in which the liquid jet forms a jet may be liquid, gas, solid such as powder or pulp, or a mixture thereof, as long as it is in a fluid state. Furthermore, if necessary, another fluid such as carbon dioxide gas can be added to the above fluid as a new fluid. The fluid and the new fluid may be uniformly mixed and jetted, or may be jetted separately.

A liquid jet is a liquid or a jet of fluid in which solid particles or gas is dispersed or mixed in the liquid, and refers to a liquid jet containing raw material slurry of pulp or inorganic particles or air bubbles. The gas referred to here may contain bubbles due to cavitation.

Flow velocity and pressure are particularly important because cavitation occurs when a liquid is accelerated and the local pressure is lower than the liquid's vapor pressure. For this reason, the basic dimensionless number representing the cavitation state, the cavitation number (Cavitation Number) σ, is preferably 0.001 or more and 0.5 or less, and more preferably 0.003 or more and 0.2 or less. It is preferably 0.01 or more and 0.1 or less, particularly preferably. When the cavitation number σ is less than 0.001, the pressure difference with the surroundings when the cavitation bubble collapses is low, so the effect is small. less likely to occur.

Further, when cavitation is generated by injecting the injection liquid through a nozzle or an orifice pipe, the pressure of the injection liquid (upstream pressure) is desirably 0.01 MPa or more and 30 MPa or less, and 0.7 MPa or more and 20 MPa or less. 2 MPa or more and 15 MPa or less is more preferable. If the upstream pressure is less than 0.01 MPa, it is difficult to generate a pressure difference with the downstream pressure, and the effect is small. On the other hand, when the pressure is higher than 30 MPa, a special pump and pressure vessel are required, and the energy consumption increases, which is disadvantageous in terms of cost. On the other hand, the pressure in the container (downstream pressure) is preferably 0.005 MPa or more and 0.9 MPa or less in terms of static pressure. Also, the ratio of the pressure in the container to the pressure of the injection liquid is preferably in the range of 0.001 to 0.5.

In the present invention, the inorganic particles can also be synthesized by injecting the injection liquid under conditions that do not generate cavitation bubbles. Specifically, the pressure of the injection liquid (upstream pressure) is set to 2 MPa or less, preferably 1 MPa or less, and the pressure of the injection liquid (downstream pressure) is more preferably set to 0.05 MPa or less.

The jet velocity of the liquid jet is preferably in the range of 1 m/sec to 200 m/sec, more preferably in the range of 20 m/sec to 100 m/sec. If the velocity of the jet is less than 1 m/sec, the effect is weak because the pressure drop is low and cavitation is less likely to occur. On the other hand, if it is more than 200 m/sec, a high pressure is required and a special device is required, which is disadvantageous in terms of cost.

In the present invention, cavitation may be generated in a reaction vessel for synthesizing inorganic particles. In addition, it is possible to process in one pass, but it is also possible to circulate as many times as necessary. Furthermore, multiple generators can be used to process in parallel or in sequence.

The injection of liquid for generating cavitation may be done in a container open to the atmosphere, but is preferably done in a pressure vessel to control cavitation.

When cavitation is generated by liquid injection, the solid content concentration of the reaction solution is preferably 30% by weight or less, more preferably 20% by weight or less. This is because such a concentration makes it easier for the cavitation bubbles to act uniformly on the reaction system. Further, the aqueous suspension of slaked lime, which is the reaction solution, preferably has a solid content concentration of 0.1% by weight or more from the viewpoint of reaction efficiency.

In the present invention, when synthesizing composite fibers of calcium carbonate and cellulose fibers, for example, the pH of the reaction solution is basic at the start of the reaction, but changes to neutral as the carbonation reaction progresses. Therefore, the reaction can be controlled by monitoring the pH of the reaction solution.

In the present invention, by increasing the injection pressure of the liquid, the flow velocity of the injection liquid increases, the pressure decreases accordingly, and stronger cavitation can be generated. In addition, by increasing the pressure in the reaction vessel, the pressure in the region where the cavitation bubbles collapse increases, and the pressure difference between the bubbles and the surroundings increases, so the bubbles collapse violently and the impact force can be increased. Furthermore, dissolution and dispersion of introduced carbon dioxide gas can be promoted. The reaction temperature is preferably 0° C. or higher and 90° C. or lower, and particularly preferably 10° C. or higher and 60° C. or lower. In general, the impact force is considered to be maximum at the midpoint between the melting point and the boiling point. Therefore, a high effect can be obtained within the above range.

When producing the conjugate fiber of the present invention, various known auxiliary agents can be added. For example, chelating agents can be added, specifically polyhydroxycarboxylic acids such as citric acid, malic acid and tartaric acid, dicarboxylic acids such as oxalic acid, sugar acids such as gluconic acid, iminodiacetic acid, ethylenediamine tetra Aminopolycarboxylic acids such as acetic acid and alkali metal salts thereof, alkali metal salts of polyphosphoric acids such as hexametaphosphoric acid and tripolyphosphoric acid, amino acids such as glutamic acid and aspartic acid and alkali metal salts thereof, acetylacetone, methyl acetoacetate, acetoacetic acid Examples include ketones such as allyl, sugars such as sucrose, and polyols such as sorbitol. In addition, as surface treatment agents, 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 acids and abietic acid, their salts, esters and ethers, and alcohol-based Active agents, sorbitan fatty acid esters, amide-based and amine-based surfactants, polyoxyalkylene alkyl ethers, polyoxyethylene nonylphenyl ether, sodium alpha olefin sulfonate, long-chain alkylamino acids, amine oxides, alkylamines, quaternary Secondary ammonium salts, aminocarboxylic acids, phosphonic acids, polyvalent carboxylic acids, condensed phosphoric acids and the like can be added. Moreover, a dispersing agent can also be used as needed. 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, methacrylic acid-polyethylene glycol. Monomethacrylate copolymer ammonium salt, polyethylene glycol monoacrylate, and the like. These can be used singly or in combination. Moreover, the timing of addition may be before or after the synthesis reaction. Such additives can be added in an amount of preferably 0.001 to 20%, more preferably 0.1 to 10%, relative to the inorganic particles.

Moreover, in the present invention, the reaction can be a batch reaction or a continuous reaction. Generally, batch reaction processes are preferred for the convenience of venting post-reaction residue. The scale of the reaction is not particularly limited, but the reaction may be performed on a scale of 100 L or less, or on a scale of more than 100 L. The size of the reaction vessel can be, for example, about 10 L to 100 L, or about 100 L to 1000 L.

Further, the reaction can be controlled by the conductivity of the reaction liquid and the reaction time. Specifically, the reaction can be controlled by adjusting the residence time of the reactant in the reaction vessel. In addition, in the present invention, the reaction can also be controlled by stirring the reaction solution in the reaction vessel or performing a multi-step reaction.

In the present invention, the conjugate fiber, which is a reaction product, is obtained as a suspension, so that it can be stored in a storage tank or subjected to treatments such as concentration, dehydration, pulverization, classification, aging, and dispersion, if necessary. can do. These can be carried out according to known processes, and may be appropriately determined in consideration of usage, energy efficiency, and the like. For example, the concentration/dehydration treatment is performed using a centrifugal dehydrator, a sedimentation concentration machine, or the like. Examples of this centrifugal dehydrator include decanters and screw decanters. When using a filter or dehydrator, there is no particular limitation on the type thereof, and common ones can be used. A calcium carbonate cake can be obtained by suitably using a vacuum drum dehydrator such as an Oliver filter. Grinding methods include ball mills, sand grinder mills, impact mills, high pressure homogenizers, low pressure homogenizers, dyno mills, ultrasonic mills, Kanda grinders, attritors, stone mills, vibration mills, cutter mills, jet mills, disaggregators, and beaters. , short-screw extruders, twin-screw extruders, ultrasonic stirrers, household juicer mixers, and the like. Classification methods include sieves such as meshes, outward-type or inward-type slit or round-hole screens, vibrating screens, heavy-duty foreign matter cleaners, light-weight foreign matter cleaners, reverse cleaners, sieving testers, and the like. Dispersion methods include a high-speed disperser and a low-speed kneader.

The conjugate fiber in the present invention can be blended with a filler or pigment in a suspension state without being completely dehydrated, but can also be dried and powdered. The dryer in this case is also not particularly limited, but for example, a flash dryer, a band dryer, a spray dryer, or the like can be preferably used.

The conjugate fiber of the present invention can be modified by known methods. For example, in some embodiments, the surface can be made hydrophobic to enhance miscibility with resins and the like.

In the present invention, water is used for preparation of the suspension, etc. As this water, ordinary tap water, industrial water, ground water, well water, etc. can be used, as well as ion-exchanged water, distilled water, ultra Pure water, industrial wastewater, and water obtained when separating and dehydrating the reaction solution can be preferably used.

Further, in the present invention, the reaction liquid in the reaction vessel can be circulated for use. By circulating the reaction solution in this manner and promoting stirring of the solution, the reaction efficiency is increased, making it easier to obtain desired composite fibers of inorganic particles and fibers.

Inorganic Particles In the present invention, inorganic particles to be combined with fibers are not particularly limited, but inorganic particles that are insoluble or sparingly soluble in water are preferred. In some cases, inorganic particles are synthesized in an aqueous system, and fiber composite fibers are sometimes used in an aqueous system, so it is preferable that the inorganic particles are insoluble or sparingly soluble in water.

The term "inorganic particles" as used herein means a compound of a metallic element or a non-metallic element. Compounds of metal elements include metal cations (eg, Na ⁺ , Ca ²⁺ , Mg ²⁺ , Al ³⁺ , Ba ²⁺ ) and anions (eg, O ²⁻ , OH ⁻ , CO ₃ ²⁻ , PO ₄ ³⁻ , SO ₄ ²⁻ , NO ₃ ⁻ , Si ₂ O ₃ ²⁻ , SiO ₃ ²⁻ , Cl ⁻ , F ⁻ , S ²⁻ etc.) are combined through ionic bonds, and are generally called inorganic salts. say something A compound of a non-metallic element is silicic acid (SiO ₂ ) or the like. In the present invention, at least part of the inorganic particles are metal salts of calcium, magnesium or barium, or at least part of the inorganic particles are metal salts of silicic acid or aluminum, or titanium, copper, silver, iron, manganese , cerium or zinc.

A method for synthesizing these inorganic particles may be a known method, and may be either a gas-liquid method or a liquid-liquid method. An example of the gas-liquid method is the carbon dioxide method. For example, magnesium carbonate can be synthesized by reacting magnesium hydroxide and carbon dioxide. Examples of the liquid-liquid method include reacting an acid (hydrochloric acid, sulfuric acid, etc.) and a base (sodium hydroxide, potassium hydroxide, etc.) by neutralization, reacting an inorganic salt with an acid or base, and reacting inorganic salts with each other. A method of causing a reaction can be mentioned. For example, barium sulfate is obtained by reacting barium hydroxide with sulfuric acid, aluminum hydroxide is obtained by reacting aluminum sulfate with sodium hydroxide, and calcium and aluminum are obtained by reacting calcium carbonate with aluminum sulfate. Composite inorganic particles can be obtained. In addition, when synthesizing inorganic particles in this way, any metal or non-metal compound can coexist in the reaction solution. In this case, the metal or non-metal compound can be efficiently incorporated into the inorganic particles. , can be compounded. For example, composite particles of calcium phosphate and titanium can be obtained by allowing titanium dioxide to coexist in the reaction solution when phosphoric acid is added to calcium carbonate to synthesize calcium phosphate.

(calcium carbonate)
In the case of synthesizing calcium carbonate, for example, calcium carbonate can be synthesized by a carbon dioxide method, a soluble salt reaction method, a lime/soda method, a soda method, or the like. In a preferred embodiment, calcium carbonate is synthesized by a carbon dioxide method. Synthesize.

In general, when producing calcium carbonate by the carbon dioxide method, lime is used as a calcium source, and water is added to quicklime CaO to obtain slaked lime Ca(OH) ₂ , and a slaked lime is added to carbon dioxide CO ₂ Calcium carbonate is synthesized by the carbonation step of blowing to obtain calcium carbonate _CaCO3 . At this time, a suspension of slaked lime prepared by adding water to quicklime may be passed through a screen to remove low-soluble lime grains contained in the suspension. Alternatively, slaked lime may be directly used as a calcium source. When synthesizing calcium carbonate by the carbon dioxide gas method in the present invention, the carbonation reaction can also be carried out in the presence of cavitation bubbles.

When calcium carbonate is synthesized by the carbon dioxide gas method, the solid content concentration of the aqueous suspension of slaked lime is preferably 0.1 to 40% by weight, more preferably 0.5 to 30% by weight, and still more preferably 1 to 20%. % by weight. If the solid content concentration is low, the reaction efficiency will be low and the production cost will be high. In the present invention, since calcium carbonate is synthesized in the presence of cavitation bubbles, even if a suspension (slurry) with a high solid content concentration is used, the reaction liquid and carbon dioxide gas can be suitably mixed.

As the aqueous suspension containing slaked lime, those commonly used in calcium carbonate synthesis can be used, for example, slaked lime is mixed with water to prepare it, or quicklime (calcium oxide) is slaked (digested) with water. can be prepared by Conditions for slaking are not particularly limited, but for example, the concentration of CaO is 0.05% by weight or more, preferably 1% by weight or more, and the temperature is 20 to 100°C, preferably 30 to 100°C. . Also, the average residence time in the slaking reaction tank (slaker) is not particularly limited, but can be, for example, 5 minutes to 5 hours, preferably 2 hours or less. Of course, the slaker may be batch or continuous. In the present invention, the carbonation reaction tank (carbonator) and the slaked reaction tank (slaker) may be separated, or one reaction tank may be used as both the carbonation reaction tank and the slaked reaction tank. good.

In the synthesis of calcium carbonate, the higher the concentration of raw materials (Ca ions, _CO3 ions) in the reaction solution and the higher the temperature, the more likely the nucleation reaction proceeds. Under such conditions, the nuclei are less likely to be fixed to the cellulose fibers, and inorganic particles released in the suspension are likely to be synthesized. Therefore, it is necessary to appropriately control the nucleation reaction in order to produce composite fibers in which calcium carbonate is strongly bound. Specifically, this can be achieved by optimizing the Ca ion and pulp concentrations and slowing the CO ₂ supply rate per hour. For example, the Ca ion concentration in the reaction vessel is preferably 0.01 mol/L or more and less than 0.20 mol/L. If it is less than 0.01 mol/L, the reaction will not progress easily, and if it is 0.20 mol/L or more, free inorganic particles in the suspension will easily be synthesized. The pulp concentration is preferably 0.5% or more and less than 4.0%. If the content is less than 0.5%, the raw materials collide with the fibers less frequently, so that the reaction does not progress easily. The amount of CO ₂ supplied per hour is desirably 0.001 mol/min or more and less than 0.060 mol/min per 1 L of the reaction solution. When it is less than 0.001 mol/min, the reaction hardly progresses, and when it is 0.060 mol/min or more, free inorganic particles are easily synthesized in the suspension.

(magnesium carbonate)
When synthesizing magnesium carbonate, a method for synthesizing magnesium carbonate can be according to a known method. For example, magnesium bicarbonate can be synthesized from magnesium hydroxide and carbon dioxide gas, and basic magnesium carbonate can be synthesized from magnesium bicarbonate via normal magnesium carbonate. Magnesium carbonate can be obtained as magnesium bicarbonate, normal magnesium carbonate, basic magnesium carbonate, etc. by a synthesis method, but it is particularly preferable to use basic magnesium carbonate as the magnesium carbonate related to the fiber composite fiber of the present invention. This is because magnesium bicarbonate has relatively low stability, and normal magnesium carbonate, which is a columnar (needle) crystal, may be difficult to fix to fibers. On the other hand, by chemically reacting even basic magnesium carbonate in the presence of fibers, it is possible to obtain a fiber composite fiber of magnesium carbonate and fibers coated with scales on the fiber surface.

Further, in the present invention, the reaction liquid in the reaction vessel can be circulated for use. By circulating the reaction liquid in this way and increasing the contact between the reaction liquid and carbon dioxide gas, the reaction efficiency is increased, and the desired inorganic particles can be easily obtained.

In the present invention, a gas such as carbon dioxide (carbon dioxide gas) is blown into the reaction vessel and can be mixed with the reaction solution. According to the present invention, carbon dioxide gas can be supplied to the reaction liquid without a gas supply device such as a fan or blower, and furthermore, the reaction can be efficiently carried out because the carbon dioxide gas is finely divided by the cavitation bubbles. .

In the present invention, the carbon dioxide concentration of the gas containing carbon dioxide is not particularly limited, but a higher carbon dioxide concentration is preferred. Also, the amount of carbon dioxide introduced into the injector is not limited and can be selected as appropriate.

The carbon dioxide-containing gas of the present invention may be substantially pure carbon dioxide gas or may be a mixture with other gases. For example, in addition to carbon dioxide gas, gases containing inert gases such as air and nitrogen can be used as gases containing carbon dioxide. As the gas containing carbon dioxide, in addition to carbon dioxide gas (carbon dioxide gas), exhaust gases discharged from incinerators, coal boilers, heavy oil boilers, etc. in paper mills can be suitably used as carbon dioxide-containing gases. In addition, the carbonation reaction can also be performed using carbon dioxide generated from the lime calcination process.

In the synthesis of magnesium carbonate, the higher the concentration of raw materials (Mg ions, _CO3 ions) in the reaction solution and the higher the temperature, the more likely the nucleation reaction proceeds. Under such conditions, the nuclei are less likely to be fixed to the cellulose fibers, and inorganic particles released in the suspension are likely to be synthesized. Therefore, it is necessary to appropriately control the nucleation reaction in order to produce composite fibers in which magnesium carbonate is strongly bound. Specifically, this can be achieved by optimizing the Mg ion and pulp concentrations and slowing the CO ₂ supply rate per hour. For example, the Mg ion concentration in the reaction vessel is preferably 0.0001 mol/L or more and less than 0.20 mol/L. If it is less than 0.0001 mol/L, the reaction will not progress easily, and if it is 0.20 mol/L or more, free inorganic particles in the suspension will easily be synthesized. The pulp concentration is preferably 0.5% or more and less than 4.0%. If the content is less than 0.5%, the raw materials collide with the fibers less frequently, so that the reaction does not progress easily. The amount of CO ₂ supplied per hour is desirably 0.001 mol/min or more and less than 0.060 mol/min per 1 L of the reaction solution. When it is less than 0.001 mol/min, the reaction hardly progresses, and when it is 0.060 mol/min or more, free inorganic particles are easily synthesized in the suspension.

(barium sulfate)
When synthesizing barium sulfate, it is an ionic crystalline compound composed of barium ions represented by barium sulfate (BaSO ₄ ) and sulfate ions. be. Pure barium sulfate is a colorless crystal, but if it contains impurities such as iron, manganese, strontium, and calcium, it becomes yellowish brown or blackish gray and translucent. It can be obtained as a natural mineral, but it can also be synthesized through chemical reactions. In particular, products synthesized by chemical reactions are used for medical purposes (X-ray contrast agents), and are also widely used for paints, plastics, storage batteries, etc. by applying their chemically stable properties.

In the present invention, composite fibers of barium sulfate and fibers can be produced by synthesizing barium sulfate in solution in the presence of fibers. Examples thereof include a method of reacting an acid (such as sulfuric acid) and a base by neutralization, a method of reacting an inorganic salt with an acid or a base, and a method of reacting inorganic salts with each other. For example, barium sulfate can be obtained by reacting barium hydroxide with sulfuric acid or aluminum sulfate, or barium sulfate can be precipitated by adding barium chloride to an aqueous solution containing sulfate.

In the synthesis of barium sulfate, the higher the concentration of raw materials (Ba ions, SO ₄ ions) in the solution and the higher the temperature, the more likely the nucleation reaction proceeds. Under these conditions, the nuclei are less likely to be fixed to the cellulose fibers, and inorganic particles released in the suspension are likely to be synthesized. Therefore, it is necessary to appropriately control the nucleation reaction in order to produce composite fibers in which barium sulfate is strongly bound. Specifically, this can be achieved by optimizing the concentrations of Ba ions and pulp and slowing down the amount of SO ₄ ions supplied per hour. For example, the Ba ion concentration in the reaction vessel is preferably 0.01 mol/L or more and less than 0.20 mol/L. If it is less than 0.01 mol/L, the reaction will not progress easily, and if it is 0.20 mol/L or more, free inorganic particles in the suspension will easily be synthesized. The pulp concentration is preferably 0.5% or more and less than 4.0%. If the content is less than 0.5%, the raw materials collide with the fibers less frequently, so that the reaction does not progress easily. The amount of SO ₄ ions supplied per hour is desirably 0.005 mol/min or more and less than 0.080 mol/min per liter of the reaction solution. When it is less than 0.001 mol/min, the reaction hardly progresses, and when it is 0.080 mol/min or more, free inorganic particles are easily synthesized in the suspension.

(hydrotalcite)
When synthesizing hydrotalcite, a known method can be used for synthesizing hydrotalcite. For example, fibers are immersed in a carbonate aqueous solution and an alkaline solution (such as sodium hydroxide) containing carbonate ions constituting an intermediate layer in a reaction vessel, and then an acid solution (divalent metal ions and trivalent metal ions constituting the basic layer). A metal salt aqueous solution containing metal ions) is added, and the temperature, pH, etc. are controlled, and a coprecipitation reaction is performed to synthesize hydrotalcite. In addition, 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. and an alkaline solution (sodium hydroxide, etc.) are added dropwise, and the temperature, pH, etc. are controlled, and a coprecipitation reaction can be performed to synthesize hydrotalcite. Although the reaction is generally carried out under normal pressure, there is also a method of hydrothermal reaction using an autoclave or the like (JP-A-60-6619).

In the present invention, various chlorides, sulfides, nitrates, and sulfates of magnesium, zinc, barium, calcium, iron, copper, cobalt, nickel, and manganese are used as a source of divalent metal ions constituting the basic layer. can be used. Various chlorides, sulfides, nitrates, and sulfates of aluminum, iron, chromium, and gallium can be used as a source of trivalent metal ions constituting the basic layer.

In the present invention, carbonate ions, nitrate ions, chloride ions, sulfate ions, phosphate ions, and the like can be used as interlayer anions. Sodium carbonate is used as the source when carbonate is the interlayer anion. However, sodium carbonate can be replaced by a gas containing carbon dioxide (carbon dioxide gas), and may be substantially pure carbon dioxide gas or a mixture with other gases. For example, exhaust gases discharged from paper mill incinerators, coal boilers, heavy oil boilers, etc. can be suitably used as the carbon dioxide-containing gas. In addition, the carbonation reaction can also be performed using carbon dioxide generated from the lime calcination process.

In the synthesis of hydrotalcite, the higher the concentration of raw materials (metal ions, _CO3 ions, etc. that make up the basic layer) in the solution and the higher the temperature, the more likely the nucleation reaction proceeds. Under these conditions, when producing composite fibers, nuclei are less likely to be fixed to the cellulose fibers, and inorganic particles liberated in the suspension are likely to be synthesized. Therefore, in order to produce composite fibers in which hydrotalcite is strongly bound, it is necessary to appropriately control the nucleation reaction. Specifically, this can be achieved by optimizing the CO ₃ ion and pulp concentrations and slowing the metal ion supply rate per hour. For example, the CO ₃ ion concentration in the reaction vessel is preferably 0.01 mol/L or more and less than 0.80 mol/L. If it is less than 0.01 mol/L, the reaction does not proceed easily, and if it is 0.80 mol/L or more, free inorganic particles are likely to be synthesized in the suspension. The pulp concentration is preferably 0.5% or more and less than 4.0%. If the content is less than 0.5%, the raw materials collide with the fibers less frequently, so that the reaction does not progress easily. The amount of metal ions supplied per hour depends on the type of metal. Less than 0.005 mol/min is more desirable. When it is less than 0.001 mol/min, the reaction hardly progresses, and when it is 0.010 mol/min or more, free inorganic particles are easily synthesized in the suspension.

(alumina/silica)
When synthesizing alumina and/or silica, a method for synthesizing alumina and/or silica may be a known method. When one or more of inorganic acids and aluminum salts are used as starting materials for the reaction, alkali silicate salts are added for synthesis. It is possible to synthesize by using an alkali silicate as a starting material and adding one or more of an inorganic acid or an aluminum salt, but the use of an inorganic acid and/or an aluminum salt as a starting material is preferable The fixation of the material to the fibers is good. The inorganic acid is not particularly limited, and for example, sulfuric acid, hydrochloric acid, nitric acid, etc. can be used. Among these, sulfuric acid is particularly preferred from the viewpoint of cost and handling. Examples of aluminum salts include aluminum sulfate, aluminum chloride, polyaluminum chloride, alum, potassium alum, etc. Among them, aluminum sulfate can be preferably used. Alkaline silicates include sodium silicate and potassium silicate, and sodium silicate is preferred because it is readily available. The molar ratio of silicic acid and alkali may be any, but generally No. 3 silicic acid in circulation has a molar ratio of SiO2:Na2O=3 to 3.4:1, which is preferably used. can.

In the present invention, in producing a composite fiber having silica and/or alumina attached to the fiber surface, silica and/or alumina are synthesized on the fiber while maintaining the pH of the reaction liquid containing the fiber at 4.6 or less. is preferred. Although the details of the reason why a composite fiber having a well-coated fiber surface is obtained by this method have not been completely clarified, since the rate of ionization to trivalent aluminum ions increases by keeping the pH low, It is thought that a composite fiber having a high coverage rate and a high fixation rate can be obtained.

In silica and/or alumina synthesis, the higher the concentration of raw materials (silicate ions, aluminum ions) in the reaction solution and the higher the temperature, the more likely the nucleation reaction proceeds. Under such conditions, the nuclei are less likely to be fixed to the cellulose fibers, and inorganic particles released in the suspension are likely to be synthesized. Therefore, in order to produce composite fibers in which silica and/or alumina are strongly bound, it is necessary to appropriately control the nucleation reaction. Specifically, this can be achieved by optimizing the pulp density and slowing the amount of silicate ions and aluminum ions to be added per unit time supplied. For example, the pulp concentration is preferably 0.5% or more and less than 4.0%. If the content is less than 0.5%, the raw materials collide with the fibers less frequently, so that the reaction does not progress easily. The amount of silicate ions and aluminum ions to be added per hour is preferably 0.001 mol/min or more, more preferably 0.01 mol/min or more, or 0.5 mol/min, per liter of the reaction solution, for example, in the case of aluminum ions. Less than min is desirable, and less than 0.050 mol/min is more desirable. If it is less than 0.001 mol/min, the reaction will not progress easily, and if it is 0.050 mol/min or more, free inorganic particles in the suspension will easily be synthesized.

As one preferred embodiment, the average primary particle size of the inorganic particles in the composite fiber of the present invention can be, for example, 1.5 μm or less, but the average primary particle size can also be 1200 nm or less or 900 nm or less, Furthermore, the average primary particle size can be 200 nm or less or 150 nm or less. Also, the average primary particle size of the inorganic particles can be 10 nm or more. The average primary particle size can be measured using an electron micrograph.

(aluminum hydroxide)
Aluminum hydroxide is an ionic crystalline compound composed of aluminum ions represented by Al(OH) ₃ and hydroxide ions, and is often in the form of granules and is sparingly soluble in water. Products synthesized through chemical reactions are used for pharmaceuticals and adsorbents, and are also used as flame retardants and non-combustible agents by utilizing the property of releasing water when heated.

In the present invention, composite fibers of aluminum hydroxide and fibers can be produced by synthesizing aluminum hydroxide in a solution in the presence of fibers. Examples thereof include a method of reacting an acid (such as sulfuric acid) and a base by neutralization, a method of reacting an inorganic salt with an acid or a base, and a method of reacting inorganic salts with each other. For example, aluminum hydroxide can be obtained by reacting sodium hydroxide and aluminum sulfate, or aluminum hydroxide can be precipitated by adding aluminum chloride to an aqueous solution containing an alkali salt.

In the synthesis of aluminum hydroxide, the higher the concentration of raw materials (Al ions, OH ions) in the solution and the higher the temperature, the more likely the nucleation reaction proceeds. Under these conditions, the nuclei are less likely to be fixed to the cellulose fibers, and inorganic particles released in the suspension are likely to be synthesized. Therefore, it is necessary to appropriately control the nucleation reaction in order to produce composite fibers in which aluminum hydroxide is strongly bound. Specifically, this can be achieved by optimizing the concentrations of OH ions and pulp and slowing the amount of Al ions supplied per hour. For example, the OH ion concentration in the reaction vessel is preferably 0.01 mol/L or more and less than 0.50 mol/L. If it is less than 0.01 mol/L, the reaction will not progress easily, and if it is 0.50 mol/L or more, free inorganic particles are likely to be synthesized in the suspension. The pulp concentration is preferably 0.5% or more and less than 4.0%. If the content is less than 0.5%, the raw materials collide with the fibers less frequently, so that the reaction does not progress easily. The amount of Al ions supplied per hour is desirably 0.001 mol/min or more and less than 0.050 mol/min per liter of the reaction solution. If it is less than 0.001 mol/min, the reaction will not progress easily, and if it is 0.050 mol/min or more, free inorganic particles in the suspension will easily be synthesized.

Cellulose Fiber The composite fiber used in the present invention is a composite of cellulose fiber and inorganic particles. As the cellulose fibers constituting the composite fibers, for example, natural cellulose fibers, as well as regenerated fibers (semi-synthetic fibers) such as rayon and lyocell, and synthetic fibers can be used without limitation. Examples of raw materials for cellulose fibers include pulp fibers (wood pulp and non-wood pulp), cellulose nanofibers, bacterial cellulose, animal-derived cellulose such as sea squirts, and algae. Wood pulp is produced by pulping wood raw materials. Just do it. Wood raw materials include red pine, black pine, Sakhalin fir, spruce, red pine, larch, fir, hemlock, cedar, cypress, larch, white fir, spruce, hiba, Douglas fir, hemlock, white fir, spruce, balsam fir, cedar, pine, Coniferous trees such as Mercury pine and radiata pine, and mixtures of these, broadleaf trees such as beech, birch, alder, oak, tab, chinensis, white birch, cotton willow, poplar, ash, willow, eucalyptus, mangrove, lauan, and acacia, and mixtures thereof material is exemplified.

The method of pulping natural materials such as wood raw materials (woody raw materials) is not particularly limited, and examples thereof include pulping methods commonly used in the paper industry. Wood pulp can be classified by pulping method, for example, chemical pulp cooked by methods such as Kraft method, sulfite method, soda method, polysulfide method; mechanical pulp obtained by mechanical power such as refiner and grinder; semi-chemical pulp obtained by mechanical pulping after pretreatment with a cellulose; waste paper pulp; deinked pulp, and the like. The wood pulp may be unbleached (before bleaching) or bleached (after bleaching).

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

The pulp fibers may be either unbeaten or beaten, and may be selected depending on the physical properties of the composite fiber sheet, but beating is preferred. As a result, improvement in sheet strength and promotion of fixation of inorganic particles can be expected.

In addition, these cellulose raw materials are further processed to obtain powdered cellulose, chemically modified cellulose such as oxidized cellulose, and cellulose nanofibers: CNF (microfibrillated cellulose: MFC, TEMPO-oxidized CNF, phosphorylated CNF, carboxymethylated CNF, mechanical pulverized CNF, etc.) can also be used. As the powdered cellulose used in the present invention, for example, an undegraded residue obtained after acid hydrolysis of selected pulp is purified, dried, pulverized, and sieved. A crystalline cellulose powder having a distribution may be used, or commercially available products such as KC Floc (manufactured by Nippon Paper Industries), Ceorus (manufactured by Asahi Kasei Chemicals), and Avicel (manufactured by FMC) may be used. The degree of polymerization of cellulose in powdered cellulose is preferably about 100 to 1500, the crystallinity of powdered cellulose by X-ray diffraction method is preferably 70 to 90%, and the volume average particle diameter by laser diffraction particle size distribution analyzer. is preferably 500 nm or more and 100 μm or less.

The oxidized cellulose used in the present invention can be obtained, for example, by oxidation in water using an oxidizing agent in the presence of an N-oxyl compound and a compound selected from the group consisting of bromides, iodides, or mixtures thereof. can. As cellulose nanofibers, a method of defibrating the above 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 by a refiner, a high-pressure homogenizer, a grinder, a uniaxial or multiaxial kneader, a bead mill, or the like. A method of defibrating can be used. 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 electron microscope observation or the like, and is preferably in the range of 5 nm to 300 nm, for example. When producing the cellulose nanofibers, before and/or after defibrating and/or refining the cellulose, an optional compound may be further added to react 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, heptanoyl group, octanoyl group, nonanoyl group , decanoyl group, undecanoyl group, dodecanoyl group, myristoyl group, palmitoyl group, stearoyl group, pivaloyl group, benzoyl group, naphthoyl group, nicotinoyl group, isonicotinoyl group, furoyl group, acyl group such as cinnamoyl group, 2-methacryloyloxyethyl isocyanate 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 group, undecyl group, dodecyl group, myristyl group, palmityl group, alkyl group such as stearyl group, oxirane group, oxetane group, oxyl group, thiirane group, thietane group and the like. Hydrogen in these substituents may be substituted with a functional group such as a hydroxyl group or a carboxyl group. Moreover, a part of the alkyl group may be an unsaturated bond. The compounds used to introduce these functional groups are not particularly limited, and examples thereof include compounds having a group derived from phosphoric acid, compounds having a group derived from carboxylic acid, compounds having a group derived from sulfuric acid, and compounds derived from sulfonic acid. group, a compound having an alkyl group, a compound having an amine-derived group, and the like. The compound having a phosphate group is not particularly limited, but examples thereof include phosphoric acid and lithium salts of phosphoric acid such as lithium dihydrogen phosphate, dilithium hydrogen phosphate, trilithium phosphate, lithium pyrophosphate, and lithium polyphosphate. . Furthermore, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate and sodium polyphosphate, which are sodium salts of phosphoric acid, may be mentioned. Furthermore, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, potassium pyrophosphate, and potassium polyphosphate, which are potassium salts of phosphoric acid, may be mentioned. Furthermore, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, ammonium polyphosphate, etc., which are ammonium salts of phosphoric acid, can be used. Among these, phosphoric acid, sodium salt of phosphoric acid, potassium salt of phosphoric acid, and ammonium salt of phosphoric acid are preferable from the viewpoint of high efficiency of introduction of phosphoric acid group and easy industrial application, and sodium dihydrogen phosphate. , Disodium hydrogen phosphate is more preferable, but not particularly limited. The compound having a carboxyl group is not particularly limited, but includes 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. . Acid anhydrides of compounds having a carboxyl group are not particularly limited, but include acid anhydrides of dicarboxylic acid compounds such as maleic anhydride, succinic anhydride, phthalic anhydride, glutaric anhydride, adipic anhydride, and itaconic anhydride. be done. Derivatives of compounds having a carboxyl group are not particularly limited, but include imidized acid anhydrides of compounds having a carboxyl group and derivatives of acid anhydrides of compounds having a carboxyl group. Examples of imidized acid anhydrides of compounds having a carboxyl group include, but are not particularly limited to, imidized dicarboxylic acid compounds such as maleimide, succinimide and phthalimide. The acid anhydride derivative of a compound having a carboxyl group is not particularly limited. For example, at least part of the hydrogen atoms of the acid anhydride of the compound having a carboxyl group, such as dimethylmaleic anhydride, diethyl maleic anhydride, and diphenyl maleic anhydride, is a substituent (e.g., an alkyl group, a phenyl group, etc.). ) substituted with Among the compounds having a group derived from a carboxylic acid, maleic anhydride, succinic anhydride, and phthalic anhydride are preferable because they are industrially applicable and easily gasified, but are not particularly limited. In addition, the cellulose nanofibers may be modified in such a manner that the modifying compound physically adsorbs to the cellulose nanofibers without chemically bonding them. Examples of the physically adsorbable compound include surfactants, which may be anionic, cationic or nonionic. When the above modification is performed before defibrating and/or pulverizing the cellulose, these functional groups can be eliminated after defibrating and/or pulverizing to restore the original hydroxyl groups. By applying the above modifications, it is possible to accelerate the defibration of the cellulose nanofibers and facilitate mixing with various substances when using the cellulose nanofibers.

The fibers shown above may be used singly or in combination. For example, fibrous material recovered from paper mill effluents may be fed to the carbonation reaction of the present invention. By supplying such a substance to a reaction tank, various composite particles can be synthesized, and also fibrous particles can be synthesized in terms of shape.

In the present invention, in addition to fibers, substances that can be incorporated into inorganic particles as a product to form composite particles can be used. In the present invention, fibers such as pulp fibers are used, but by synthesizing inorganic particles in a solution containing inorganic particles, organic particles, polymers, etc., these substances are further incorporated. It is possible to produce composite particles with

The fiber length of the composite fibers is not particularly limited, but for example, the average fiber length can be about 0.1 μm to 15 mm, and may be 1 μm to 12 mm, 100 μm to 10 mm, 400 μm to 8 mm, and the like. Among them, in the present invention, the average fiber length is preferably 400 μm or more (0.4 mm or more).

The average fiber diameter of the fibers to be combined is not particularly limited, but for example, the average fiber diameter can be about 1 nm to 100 μm, and may be 500 nm to 100 μm, 1 μm to 90 μm, 3 μm to 50 μm, 5 μm to 30 μm. Among them, in the present invention, it is preferable that the average fiber diameter is 500 nm or more because the production efficiency in the subsequent process can be improved.

The average fiber length and average fiber diameter of fibers can be measured by a fiber length measuring device. Examples of the fiber length measuring device include Valmet Fractionator (manufactured by Valmet).

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

In a preferred embodiment, the conjugate fiber according to the present invention has inorganic particles covering 15% or more of the fiber surface, and when the cellulose fiber surface is covered with such an area ratio, the characteristics attributed to the inorganic particles are large. while the features attributed to the fiber surface become smaller.

The conjugate fiber according to the present invention can be used in various forms such as powder, pellet, mold, aqueous suspension, paste, sheet, board, block and other forms. In addition, the conjugate fiber as a main component can also be formed into a molded article such as a mold, particles, or pellets together with other materials. There are no particular restrictions on the dryer used for drying to powder, but for example, a flash dryer, band dryer, spray dryer, or the like can be preferably used.

Composite fibers according to the present invention can be used in a variety of applications, such as paper, fibers, cellulosic composite materials, filter materials, paints, plastics and other resins, rubbers, elastomers, ceramics, glass, tires, and construction. Materials (asphalt, asbestos, cement, boards, concrete, bricks, tiles, plywood, fiberboard, ceiling materials, wall materials, flooring materials, roofing materials, etc.), furniture, various carriers (catalyst carriers, pharmaceutical carriers, agricultural chemical carriers, microorganisms carriers, etc.), adsorbents (impurity removal, deodorant, dehumidification, etc.), antibacterial agents, antiviral agents, anti-wrinkle agents, clay, abrasives, friction materials, modifiers, repair materials, heat insulating materials, heat resistant materials, heat radiation materials, moisture-proof materials, water-repellent materials, water-resistant materials, light-shielding materials, sealants, shielding materials, insect repellents, adhesives, medical materials, paste materials, anti-tarnishing agents, radio-wave absorbing materials, insulating materials, sound-insulating materials, interior materials, waterproofing materials It can be widely used for various applications such as vibration materials, semiconductor sealing materials, radiation shielding materials, and materials. In addition, it can be used as various fillers, coating agents, etc. in the above applications. Among these, adsorbents, antibacterial materials, antiviral agents, friction materials, radiation shielding materials, flame retardant materials, building materials, and heat insulating materials are preferred.

The conjugate fiber of the present invention may be applied to papermaking applications such as printing paper, newsprint, inkjet paper, PPC paper, kraft paper, fine paper, coated paper, lightly coated paper, wrapping paper, thin paper, color fine paper, Paper, cast-coated paper, non-carbon paper, label paper, thermal paper, various fancy papers, water-soluble paper, release paper, casting paper, base paper for wallpaper, flame-retardant paper (non-combustible paper), base paper for laminates, printed electronic paper, Battery separator, cushion paper, tracing paper, impregnated paper, ODP paper, construction 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, cosmetic paper (oil removal paper, etc.), various sanitary papers (toilet paper, tissue paper, wipers, diapers, sanitary products, etc.), tobacco paper, paperboard (liner, core paper, white paperboard, etc.), paper plate base paper, Base paper for cups, baking paper, abrasive paper, synthetic paper, and the like. That is, according to the present invention, a composite fiber of inorganic particles and fibers having a small primary particle size and a narrow particle size distribution can be obtained. characteristics can be exhibited. Furthermore, unlike the case where the inorganic particles are simply blended with the fibers, if the inorganic particles are combined with the fibers to form a composite fiber, the inorganic particles are not only easily retained in the sheet, but also a sheet in which the inorganic particles are uniformly dispersed without agglomeration can be obtained. Obtainable. Electron microscopic observation has revealed that the inorganic particles in the present invention are not only fixed on the outer surface of the fiber and inside the lumen, but also formed inside the microfibrils in a preferred embodiment.

When using the conjugate fiber of the present invention, particles generally called inorganic fillers and organic fillers and various fibers can be used together. For example, inorganic fillers include calcium carbonate (light calcium carbonate, heavy calcium carbonate), magnesium carbonate, barium carbonate, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, zinc hydroxide, clay (kaolin, calcined kaolin, delaminated kaolin). ), talc, zinc oxide, zinc stearate, titanium dioxide, silica made from sodium silicate and mineral acids (white carbon, silica/calcium carbonate composite fiber, silica/titanium dioxide composite fiber), clay, bentonite, diatomaceous earth, Examples include calcium sulfate, zeolite, inorganic fillers that regenerate and utilize ash obtained in the deinking process, and inorganic fillers that form composite fibers with silica or calcium carbonate in the regenerating process. As the calcium carbonate-silica composite, amorphous silica such as white carbon may be used in combination with calcium carbonate and/or light calcium carbonate-silica composite. Organic fillers include urea-formalin resin, polystyrene resin, phenolic resin, hollow microparticles, acrylamide composite fibers, wood-derived substances (fine fibers, microfibril fibers, powdered kenaf), modified insolubilized starch, ungelatinized starch, etc. is mentioned. As for fibers, there are no restrictions on natural fibers such as cellulose, synthetic fibers artificially synthesized from raw materials such as petroleum, regenerated fibers (semi-synthetic fibers) such as rayon and lyocell, and inorganic fibers. can be used. In addition to the above, examples of natural fibers include protein-based fibers such as wool, silk threads and collagen fibers, and complex sugar chain-based fibers such as chitin/chitosan fibers and alginic acid fibers. Examples of cellulosic raw materials include pulp fibers (wood pulp and non-wood pulp), bacterial cellulose, animal-derived cellulose such as sea squirt, and algae. Wood pulp may be produced by pulping wood raw materials. Wood raw materials include red pine, black pine, Sakhalin fir, spruce, red pine, larch, fir, hemlock, cedar, cypress, larch, white fir, spruce, hiba, Douglas fir, hemlock, white fir, spruce, balsam fir, cedar, pine, Coniferous trees such as Mercury pine and radiata pine, and mixtures of these, broadleaf trees such as beech, birch, alder, oak, tab, chinensis, white birch, cotton willow, poplar, ash, willow, eucalyptus, mangrove, lauan, and acacia, and mixtures thereof material is exemplified. The method of pulping the wood raw material is not particularly limited, and an example is a pulping method commonly used in the paper industry. Wood pulp can be classified by pulping method, for example, chemical pulp cooked by methods such as Kraft method, sulfite method, soda method, polysulfide method; mechanical pulp obtained by mechanical power such as refiner and grinder; semi-chemical pulp obtained by mechanical pulping after pretreatment with a cellulose; waste paper pulp; deinked pulp, and the like. The wood pulp may be unbleached (before bleaching) or bleached (after bleaching). Examples of non-wood-derived pulp include cotton, hemp, sisal hemp, Manila hemp, flax, straw, bamboo, bagasse, kenaf, sugar cane, corn, rice straw, kozo, mitsumata, and the like. The wood pulp and non-wood pulp may be either unbeaten or beaten. In addition, these cellulose raw materials are further processed to obtain powdered cellulose, chemically modified cellulose such as oxidized cellulose, and cellulose nanofibers: CNF (microfibrillated cellulose: MFC, TEMPO-oxidized CNF, phosphorylated CNF, carboxymethylated It can also be used as CNF, mechanically ground CNF). Synthetic fibers include polyester, polyamide, polyolefin and acrylic fibers, semi-synthetic fibers include rayon and acetate, and inorganic fibers include glass fibers, carbon fibers and various metal fibers. Regarding the above, these may be used alone or in combination of two or more.

The average particle size, shape, etc. of the inorganic particles constituting the composite fiber of the present invention can be confirmed by observation with an electron microscope. Furthermore, by adjusting the conditions for synthesizing the inorganic particles, inorganic particles having various sizes and shapes can be formed into composite fibers with fibers.

Form of conjugate fiber In the present invention, the conjugate fiber described above can be formed into various moldings (body). For example, a high-ash sheet can be easily obtained by sheeting the composite fiber of the present invention. Also, the obtained sheets can be laminated to form a multilayer sheet.

Examples of paper machines used for sheet production include fourdrinier paper machines, cylinder paper machines, gap formers, hybrid formers, rotoformers, multi-layer paper machines, and known paper machines that combine these paper-making methods. is mentioned. Both the press linear pressure in the paper machine and the calender linear pressure in the subsequent calendering process can be determined within a range that does not interfere with the workability and the performance of the composite fiber sheet. Starch, various polymers, pigments, and mixtures thereof may be applied to the formed sheet by impregnation or coating.

A wet and/or dry paper strength agent (paper strength enhancer) may 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, polyvinylamine. , polyvinyl alcohol; composite polymers or copolymers composed of two or more of the above resins; starch and modified starch; carboxymethyl cellulose, guar gum, urea resin, and the like. The amount of the paper strength agent to be added is not particularly limited.

In addition, a high molecular weight polymer or an inorganic substance can be added in order to promote fixation of the filler to the fibers or to improve the retention of the filler or the fibers. For example, as coagulants, polyethyleneimines and modified polyethyleneimines containing tertiary and/or quaternary ammonium groups, polyalkyleneimines, dicyandiamide polymers, polyamines, polyamine/epichlorohydrin polymers, and dialkyldiallyl quaternary ammonium monomers, dialkyl Cations of aminoalkyl acrylates, dialkylaminoalkyl methacrylates, dialkylaminoalkylacrylamides, polymers of dialkylaminoalkylmethacrylamides and acrylamides, polymers of monoamines and epihalohydrin, polyvinylamines, polymers with vinylamine moieties, and mixtures thereof cation-rich amphoteric polymers obtained by copolymerizing anionic groups such as carboxyl groups and sulfone groups in the polymer molecules, and mixtures of cationic polymers and anionic or amphoteric polymers. be able to. Cationic, anionic, and amphoteric polyacrylamide-based substances can also be used as retention agents. Also, in addition to these, at least one kind of cationic or anionic polymer can be used together, so-called dual polymer retention system can be applied, and at least one kind of anionic bentonite, colloidal silica, polysilicic acid, A multi-component yield system that uses at least one type of inorganic fine particles such as polysilicic acid or polysilicate microgels and aluminum-modified products thereof, and organic fine particles having a particle size of 100 μm or less, which are so-called micropolymers obtained by cross-linking polymerization of acrylamide. good too. In particular, when the polyacrylamide-based substances used alone or in combination have a weight-average molecular weight of 2 million daltons or more as determined by the intrinsic viscosity method, a good yield can be obtained, preferably 5 million daltons or more, more preferably 5 million daltons or more. When is the above acrylamide-based substance of 10 million daltons or more and less than 30 million daltons, a very high yield can be obtained. 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 quaternary ammonium salts obtained by copolymerizing acrylic acid esters. The cationic charge density of the cationic polyacrylamide-based material is not particularly limited.

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

The basic weight of the sheet (basis weight: weight per ^square meter) can be adjusted appropriately according to the purpose. It is good because the drying load of the is low. Also, the basis weight of the sheet may be 1200 g/m ² or more, for example, 2000 to 110000 g/m ² .

It is also possible to use molding methods other than sheeting, for example, a method called pulp molding, where the raw material is poured into a mold and suction dehydrated and dried, or it is spread on the surface of a molded product such as resin or metal and dried. After that, molded articles having various shapes can be obtained by a method such as peeling from the substrate. It can also be mixed with resin and molded like plastic, or it can be mixed with cement or rubber and used as a reinforcing material. It can also be formed into a board shape or a block shape by pressure/heat press molding, which is generally used to produce inorganic boards such as cement and gypsum. In general, the sheet can be folded and rolled up, but it can be made into a board if more strength is required. Moreover, it is also possible to mold into a block shape, which is a mass with a thickness, such as a rectangular parallelepiped or a cube.

In the compounding, drying, and molding described above, only one kind of conjugated fiber can be used, or two or more kinds of conjugated fibers can be mixed and used. When two or more types of composite fibers are used, they can be mixed in advance, or they can be blended, dried, and molded, and then mixed.

Moreover, various organic substances such as polymers and various inorganic substances such as pigments may be added to the composite fiber molded article later.

Moldings produced from the product of the present invention can be printed. Although this printing method is not particularly limited, for example, offset printing, silk screen printing, screen printing, gravure printing, microgravure printing, flexographic printing, letterpress printing, sticker printing, form printing, on-demand printing, fan It can be carried out by known methods such as shear roll printing and inkjet printing. Among these, inkjet printing is preferable because it does not require the preparation of a block copy unlike offset printing, and it is relatively easy to increase the size of the inkjet printer, and printing on a large sheet is also possible. In addition, since flexographic printing can be suitably printed on a molded article having relatively large unevenness on the surface, it can be suitably used when molded into a shape such as a board, a mold, or a block.

The present invention will be described in more detail with specific experimental examples, but the present invention is not limited to the following specific examples. In addition, unless otherwise specified in this specification, concentrations, parts, etc. are based on weight, and numerical ranges are described as including their end points.

[Example 1]
Softwood bleached kraft pulp (NBKP, manufactured by Nippon Paper Industries) and hardwood bleached kraft pulp (LBKP, manufactured by Nippon Paper Industries) are put into a pulper (manufactured by IHI voite) at a ratio of 2:8, and water is added to defiberize at a concentration of 5%. , a pulp dispersion was prepared. This was beaten with a double disc refiner (DDR, manufactured by Aikawa Iron Works Co., Ltd.) until the freeness reached 410 ml.
After removing foreign matter by passing the obtained pulp dispersion through a screen (manufactured by Aikawa Iron Works Co., Ltd.), 10 m ³ was put into a reactor (manufactured by Sumitomo Heavy Industries Process Equipment Co., Ltd.), and sodium hydroxide was added while stirring at a temperature of 57 ° C. and sodium carbonate were added at 76.7% and 12.6% by pulp weight to give a pH of 13. Thereafter, a mixed solution of magnesium sulfate with a concentration of 7.3% and aluminum sulfate with a concentration of 3.4% was added dropwise over 60 minutes, and the mixture was reacted until the pH reached 7. The suspension of bicomponent fibers obtained has a concentration of 1.5%.
An antiseptic (trade name: F3-500, manufactured by Sumika Environmental Science Co., Ltd.) and an antifungal agent (trade name: ES9535, manufactured by Sumika Environmental Science Co., Ltd.) were added to this suspension. Each was added so as to be 1000 mg/L.
Next, the resulting conjugate fiber suspension was dehydrated with a dehydrator (manufactured by Fukoku Kogyo Co., Ltd.) to a concentration of 29.1% to obtain conjugate fibers. The Canadian standard freeness of the composite fiber was 413 ml, and the breakdown of the solid content in the product was as follows.
・Composite fiber (composite fiber composed of 24.0% magnesium hydrotalcite, 37.6% LBKP, and 9.4% NBKP) 71.7%
・Magnesium hydrotalcite (not fixed to pulp fibers) 29.0%
The obtained dehydrated composite fiber was packed in a flexible container and stored. When the condition was checked after 2 months, it was confirmed that there was no growth of mold and no offensive odor.

[Comparative Example 1]
The 1.5% concentration suspension of the composite fibers obtained in Example 1 was concentrated to a concentration of 29.0% using a dehydrator (manufactured by Fukoku Kogyo Co., Ltd.) without adding any preservatives or fungicides. , to obtain a composite fiber. The Canadian standard freeness of the composite fiber was 410 ml, and the breakdown of the solid content in the product was as follows.
・Composite fiber (composite fiber composed of 24.0% magnesium hydrotalcite, 37.6% LBKP, and 9.4% NBKP) 71.7%
・Magnesium hydrotalcite (not fixed to pulp fibers) 29.0%
The obtained dehydrated composite fiber was packed in a flexible container and stored. When the condition was checked after two months, it was confirmed that the exposed surface was covered with black mold and had a rotten odor.

Claims (3)

A method for storing composite fibers of fibers and inorganic particles, comprising:
adding an antifungal agent and/or a preservative to the composite fiber suspension having a concentration of 0.01 to 7% by mass;
a step of concentrating the composite fiber suspension to a concentration of 25% by mass or more;
The above method, comprising 2. The method according to claim 1, wherein the antifungal agent and/or antiseptic agent comprises an isothiazolone compound. 3. The method according to claim 1, wherein an antifungal agent and/or a preservative is added to the composite fiber suspension in an amount of 1 to 10000 mg/L.