WO2019065270A1 - Feuille multicouche et son procédé de production - Google Patents

Feuille multicouche et son procédé de production Download PDF

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Publication number
WO2019065270A1
WO2019065270A1 PCT/JP2018/033964 JP2018033964W WO2019065270A1 WO 2019065270 A1 WO2019065270 A1 WO 2019065270A1 JP 2018033964 W JP2018033964 W JP 2018033964W WO 2019065270 A1 WO2019065270 A1 WO 2019065270A1
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fibers
sheet
fiber
inorganic particles
composite
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PCT/JP2018/033964
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English (en)
Japanese (ja)
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絢香 長谷川
萌 福岡
正淳 大石
幸司 蜷川
徹 中谷
後藤　至誠
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日本製紙株式会社
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Priority to JP2019544565A priority Critical patent/JP7166263B2/ja
Publication of WO2019065270A1 publication Critical patent/WO2019065270A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes

Definitions

  • the present invention relates to a multilayer sheet including an inorganic particle composite fiber sheet, and a method for producing the same.
  • Fibers can exhibit various properties by depositing inorganic particles on their surfaces.
  • a method of producing a composite of inorganic particles and fibers has been developed by synthesizing an inorganic substance in the presence of fibers.
  • Patent Document 1 describes an inorganic particle composite fiber of calcium carbonate and lyocell fiber or polyolefin fiber.
  • the manufacturer of the multilayer sheet may want to stack another sheet in order to provide a function different from that of the partial sheet.
  • the other sheet has a function derived from the inorganic particles, if the inorganic particles can be attached to the fiber with high yield, the multilayer sheet can efficiently have the high function derived from the inorganic particles. .
  • the present invention is an invention made in view of such circumstances, and it is possible to easily laminate a multilayer sheet by laminating a sheet having another function on a certain sheet using a sheet containing inorganic particles with high yield. Intended to be provided.
  • a multilayer sheet concerning one mode of the present invention has laminated two or more sheets containing a fiber, and a sheet of at least one layer contains a composite fiber of a fiber and an inorganic particle. , Has different properties than the sheet of another layer.
  • a method for producing a multilayer sheet having properties different from those of a sheet comprising the steps of: producing a composite fiber by synthesizing inorganic particles in a slurry containing fibers, and containing the composite fiber including the composite fiber And a sheet producing step of subjecting the slurry and the slurry for forming the sheet of the other layer to a continuous paper machine to continuously make a sheet to produce a sheet.
  • FIG. 1 is a schematic view showing a schematic configuration of an open system reactor that can be used for producing a composite fiber. It is a schematic diagram which shows the schematic structure of the pressure reaction container which can be used by production
  • a multilayer sheet according to one aspect of the present invention is a laminate of two or more sheets containing fibers, and at least one sheet of the sheet contains composite fibers of fibers and inorganic particles, and is different from the sheet of another layer It has the nature.
  • the sheet of at least one layer comprises a composite fiber of fibers and inorganic particles
  • the sheet of another layer does not comprise a composite fiber of fibers and inorganic particles, or comprises a composite fiber of fibers and inorganic particles
  • the multilayer sheet according to an aspect of the present invention can be obtained by including two or more layers of the sheet and the type of inorganic particles contained in one layer being different from the type of inorganic particles contained in at least one other layer. .
  • the other sheet has a different property from the sheet determined. It is possible to produce a multilayer sheet having different properties as well as the properties of the sheet of the layer. In addition, by providing a sheet having a property of exhibiting more effect when provided on the surface layer, the function can be exhibited more. Furthermore, since it can manufacture suitably by continuous papermaking as mentioned later, it can manufacture easily.
  • the properties of the sheet may be such that the properties of the sheet of at least one layer are based on the function derived from the inorganic particles constituting the composite fiber. For example, properties such as flame retardancy, antibacterial properties, deodorizing properties, antiviral properties, radiation shielding properties and adsorptive properties can be mentioned.
  • the sheet of the separate layer may or may not contain inorganic particles.
  • the properties of the sheet of the other layer may be based on the thickness of the sheet, the structure such as basis weight, and the like.
  • the sheet of the at least one layer and the sheet of the other layer may have different properties because at least one of the type and the content of the inorganic particles to be contained is different. By adjusting the type and content of the inorganic particles that cause the sheet to exhibit the desired function, a multilayer sheet having the desired function can be manufactured more easily.
  • the number of sheets constituting the multilayer sheet according to one aspect of the present invention is not particularly limited, but, for example, sheets of 2 to 5 layers may be laminated.
  • the composite fiber not only the fibers and the inorganic particles are mixed, but the inorganic particles are less likely to be detached from the fibers because the fibers and the inorganic particles are complexed by hydrogen bonding or the like. Therefore, the inclusion of the composite fiber can provide a sheet with a high yield of inorganic particles. Since the multilayer sheet according to an aspect of the present invention includes such a sheet, it is possible to efficiently produce a multilayer sheet that expresses the function derived from the inorganic particles.
  • the binding strength between the cellulose fiber and the inorganic particles in the composite fiber can be evaluated, for example, by ash fraction (%).
  • ash fraction %
  • the composite fiber when it is in the form of a sheet, it can be evaluated by a numerical value such as (the ash content of the composite fiber before disintegration and dissolution of the sheet) ⁇ 100.
  • the composite fiber is dispersed in water to adjust the solid concentration to 0.2%, and deaggregated for 5 minutes with a standard disintegrator defined in JIS P 8220-1: 2012, according to JIS P 8222: 1998.
  • the ash retention when sheeted using a 150 mesh wire can be used for evaluation, and the ash retention is 20% by mass or more in a preferred embodiment, and the ash retention is 50% by mass or more in a more preferred embodiment is there. That is, unlike the case where inorganic particles are simply blended into fibers, when inorganic particles are complexed with fibers, for example, in the embodiment in which sheet-like composite fibers are formed, the inorganic particles are not only easily retained in composite fibers. A composite fiber uniformly dispersed without aggregation can be obtained.
  • the fiber surface in the composite fiber is covered with inorganic particles.
  • the coverage (area ratio) of the cellulose fiber with the inorganic particles is more preferably 25% or more, and further preferably 40% or more.
  • 60% or more of a coverage and 80% or more of composite fiber can be manufactured suitably.
  • the upper limit value of the coverage may be appropriately set according to the application, but is, for example, 100%, 90%, 80%.
  • the ash content (%) of the composite fiber is preferably 30% or more and 90% or less, and more preferably 40% or more and 80% or less.
  • the ash content (%) of the composite fiber is obtained by suction-filtering the slurry (3 g in terms of solid content) of the composite fiber using filter paper, then drying the residue in an oven (105 ° C., 2 hours), and further organic fraction at 525 ° C. Can be calculated from the weight before and after combustion.
  • sheets of various basis weights can be applied as a single layer sheet.
  • those having a basis weight of 30 g / m 2 or more and 600 g / m 2 or less, preferably 50 g / m 2 or more and 600 g / m 2 or less can be mentioned.
  • the inorganic particles constituting the composite fiber may be appropriately selected according to the application of the multilayer sheet, and are preferably water insoluble or poorly soluble inorganic particles. It is preferable that the inorganic particles be insoluble or poorly soluble in water, since the synthesis of the inorganic particles may be carried out in an aqueous system, and the composite fiber may be used in an aqueous system.
  • the inorganic particles are particles of inorganic compounds, and examples thereof include metal compounds.
  • Metal compounds include metal cations (eg, Na + , Ca 2+ , Mg 2+ , Al 3+ , Ba 2+, etc.) 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.) is Deki bound by ionic bond, what is commonly referred to as an inorganic salt Say.
  • Specific examples of the inorganic particles include, for example, compounds containing at least one metal selected from the group consisting of gold, silver, titanium, copper, platinum, iron, zinc, and aluminum.
  • calcium carbonate (light calcium carbonate, heavy calcium carbonate), magnesium carbonate, barium carbonate, aluminum hydroxide, calcium hydroxide, barium sulfate, magnesium hydroxide, zinc hydroxide, calcium phosphate, zinc oxide, zinc stearate, dioxide dioxide Titanium, silica (white carbon, silica / calcium carbonate composite, silica / titanium dioxide composite) manufactured from sodium silicate and mineral acid, calcium sulfate, zeolite, hydrotalcite can be mentioned.
  • amorphous silica such as white carbon may be used in combination.
  • the inorganic particles exemplified above may be used alone or in combination of two or more types, as long as they do not inhibit the reaction of synthesizing each other in the solution containing fibers.
  • the ash content of the composite fiber of hydrotalcite and cellulose fiber contains 10% by weight or more of at least one of magnesium and zinc.
  • the inorganic particles are more preferably magnesium carbonate for the purpose of obtaining a highly flame-retardant sheet, more preferably barium sulfate for the purpose of obtaining a sheet having a high radiation shielding function, and deodorizing
  • hydrotalcite is more preferable.
  • sheets having different functions may be laminated. For example, when a sheet having a deodorant or antibacterial function and a sheet having high flame retardancy are laminated, it is suitable for a partition board.
  • the average primary particle diameter of the inorganic particles can be, for example, 1 ⁇ m or less, but inorganic particles having an average primary particle diameter of 500 nm or less, inorganic particles having an average primary particle diameter of 200 nm or less, an average primary particle Inorganic particles having a particle diameter of 100 nm or less and inorganic particles having an average primary particle diameter of 50 nm or less can be used.
  • the average primary particle diameter of the inorganic particles can be 10 nm or more. The average primary particle size can be calculated from electron micrographs.
  • inorganic particles having various sizes and shapes can be complexed with fibers by adjusting the conditions for synthesizing the inorganic particles.
  • it may be a composite fiber in which scaly inorganic particles are complexed to the fiber.
  • the shape of the inorganic particles constituting the composite fiber can be confirmed by observation with an electron microscope.
  • the inorganic particles may take the form of secondary particles in which fine primary particles are aggregated, and secondary particles may be generated according to the application in the aging step, and the aggregates are pulverized by grinding.
  • the fibers constituting the composite fiber are preferably, for example, cellulose fibers.
  • cellulose fibers As a raw material of cellulose fiber, pulp fiber (wood pulp, non-wood pulp), bacterial cellulose, animal-derived cellulose such as sea squirt and algae are exemplified, and wood pulp may be manufactured by pulping wood raw material.
  • wood raw materials include red pine, black pine, todo pine, Japanese spruce, larch, fir, tsuga, tsuga, cypress, cypress, larch, silabe, spruce, hives, Douglas fir, hemlock, white fur, spruce, balsam fur, cedar, pine, Coniferous trees such as Melxi pine, Radiata pine, etc., and mixed materials thereof, hardwoods such as beech, hippopotamus, alder, larch, tub, shii, birch, poplar, taro, eucalyptus, mangrove, rawan, acacia and mixtures thereof The material is illustrated.
  • wood raw materials wood raw materials
  • wood raw materials wood raw materials
  • wood raw materials wood raw materials
  • wood pulp can be classified by the pulping method, for example, chemical pulp digested by the Kraft method, sulfite method, soda method, polysulfide method, etc .; mechanical pulp obtained by pulping by mechanical power such as refiner, grinder, etc .; Semi-chemical pulp obtained by mechanical pulping after pre-treatment by the following method; waste paper pulp; deinked pulp and the like.
  • the wood pulp may be in the unbleached (before bleaching) state or in the bleached (after bleaching) state.
  • non-wood-derived pulps examples include cotton, hemp, sisal, manila hemp, flax, persimmon, bamboo, bagasse, kenaf, sugar cane, corn, rice straw, persimmon, honey etc.
  • Pulp fibers may be either unbeaten or beaten, and may be selected according to the physical properties of the composite fiber, but it is preferable to beat. As a result, improvement in the strength of pulp fibers and promotion of fixing of inorganic particles can be expected. In addition, by refining pulp fibers, it is possible to expect the effect of improving the BET specific surface area of the composite fiber sheet in the embodiment in which a sheet-like composite fiber is obtained.
  • the degree of beating of pulp fibers can be expressed by Canadian Standard Freeness (CSF) defined in JIS P 8121-2: 2012. As the beating progresses, the drainage state of the pulp fibers decreases and the freeness becomes lower.
  • the cellulose raw material can also be used as chemically modified celluloses, such as finely pulverized cellulose and an oxidized cellulose, by further processing.
  • natural fibers include protein-based fibers such as wool, silk yarn and collagen fibers, and complex sugar chain-based fibers such as chitin / chitosan fibers and alginic acid fibers.
  • synthetic fibers include polyesters, polyamides, polyolefins, acrylic fibers, and half-fibers include rayon, lyocell, acetate and the like.
  • inorganic fibers glass fibers, carbon fibers, various metal fibers and the like can be mentioned.
  • composite fibers of synthetic fibers and cellulose fibers can also be used in one embodiment of the present invention, for example, polyesters, polyamides, polyolefins, acrylic fibers, glass fibers, carbon fibers, various metal fibers, etc. and cellulose fibers.
  • Composite fibers can also be used.
  • the fibers constituting the composite fiber are pulp fibers.
  • composite particles In addition to fibers, materials that are not directly involved in the synthesis reaction of the inorganic particles but can be incorporated into the product inorganic particles to form composite particles can be used.
  • materials that are not directly involved in the synthesis reaction of the inorganic particles but can be incorporated into the product inorganic particles to form composite particles can be used.
  • composite particles further incorporating these substances are produced by synthesizing the inorganic particles in a solution containing inorganic particles, organic particles, polymers, etc. It is possible.
  • the fibers exemplified above may be used alone or in combination of two or more.
  • the fiber length of the fibers to be complexed is not particularly limited, but for example, the average fiber length can be about 0.1 ⁇ m to 15 mm, and may be 1 ⁇ m to 12 mm, 100 ⁇ m to 10 mm, 500 ⁇ m to 8 mm, or the like.
  • the amount of fibers to be complexed is preferably such that 15% or more of the fiber surface is covered with the inorganic particles.
  • the weight ratio of fibers to inorganic particles is preferably 5/95 to 75/25, more preferably 10/90 to 70/30, and preferably 15/85 to 65/35. More preferable.
  • the composite fiber-containing slurry may contain non-complexed fibers.
  • the strength of the sheet can be improved by including fibers not forming a complex.
  • the "fiber not forming a complex" as used herein is intended to be a fiber in which inorganic particles are not complexed. It does not specifically limit as a fiber which has not formed the complex, According to the objective, it can select suitably.
  • the non-complexed fibers include various natural fibers, synthetic fibers, half fibers and inorganic fibers in addition to the fibers exemplified above.
  • natural fibers include protein-based fibers such as wool, silk yarn and collagen fibers, and complex sugar chain-based fibers such as chitin / chitosan fibers and alginic acid fibers.
  • synthetic fibers include polyesters, polyamides, polyolefins, acrylic fibers, and half-fibers include rayon, lyocell, acetate and the like.
  • inorganic fibers, glass fibers, carbon fibers, various metal fibers and the like can be mentioned.
  • composite fibers of synthetic fibers and cellulose fibers can be used as fibers which do not form a composite, and examples thereof include polyester, polyamide, polyolefin, acrylic fiber, glass fiber, carbon fiber, various metal fibers and the like.
  • Composite fibers with cellulose fibers can also be used as non-composite fibers.
  • the non-complexed fibers preferably comprise wood pulp, or preferably a combination of wood pulp and non-wood pulp and / or synthetic fibers, with wood pulp alone It is more preferable that In addition, softwood kraft pulp is more preferable because it has a long fiber length and is advantageous for improving strength.
  • the weight ratio of the composite fiber to the non-composite fiber is preferably 10/90 to 100/0, and may be 20/80 to 90/10, 30/70 to 80/20. It is preferable because the functionality of the obtained sheet is improved as the blending amount of the composite fiber is increased.
  • a sheet containing fibers is laminated in two or more layers, and at least one sheet of the sheet contains a composite fiber of fibers and inorganic particles, and a sheet of another layer And a composite fiber-containing slurry containing the composite fibers, wherein inorganic particles are synthesized in a slurry containing fibers to form the composite fibers.
  • a slurry for forming the sheet of the other layer are subjected to a continuous paper machine to continuously make a sheet to generate a sheet.
  • the composite fiber production step is a step of producing composite fibers of fibers and inorganic particles.
  • composite fibers are produced by synthesizing inorganic particles in a slurry containing fibers.
  • Method of producing composite fiber By synthesizing inorganic particles in a slurry containing fibers, it is possible to produce composite fibers in which the desired inorganic particles are complexed to the fibers.
  • Either a gas-liquid method or a liquid-liquid method may be used to synthesize inorganic particles in a slurry containing fibers.
  • An example of the gas-liquid method is the carbon dioxide method, and magnesium carbonate can be synthesized, for example, by reacting magnesium hydroxide and carbon dioxide gas. The reaction may be carried out by using a cavitation generator (see FIG. 2) or by generating ultrafine bubbles in an open system or a pressure reaction vessel.
  • FIGS. 3 and 4 Schematic diagrams of an apparatus for generating ultrafine bubbles in the open system and pressurized reaction vessels are shown in FIGS. 3 and 4, respectively.
  • an acid hydroochloric acid, sulfuric acid, etc.
  • a base sodium hydroxide, potassium hydroxide, etc.
  • barium sulfate is reacted with sulfuric acid to obtain barium sulfate
  • aluminum sulfate is reacted with sodium hydroxide to obtain aluminum hydroxide
  • calcium carbonate is reacted with aluminum sulfate to obtain calcium.
  • Inorganic particles in which aluminum and aluminum are complexed can be obtained.
  • any metal or metal compound can be made to coexist in the reaction solution, in which case the metal or metal compound is efficiently taken into the inorganic particles, and the composite Can be
  • calcium phosphate is synthesized by adding phosphoric acid to calcium carbonate
  • titanium dioxide is allowed to coexist in the reaction liquid, whereby composite particles of calcium phosphate and titanium can be obtained.
  • the synthesis reaction of one type of inorganic particle is performed in the presence of the fiber, and then the synthesis reaction is stopped to synthesize another type of inorganic particle.
  • the reaction may be carried out, or two or more kinds of inorganic particles may be simultaneously synthesized if they do not disturb each other reaction or plural types of target inorganic particles are synthesized in one reaction.
  • inorganic particles having various sizes and shapes can be complexed with the fibers.
  • it may be a composite fiber in which scaly inorganic particles are complexed to the fiber.
  • the shape of the inorganic particles constituting the composite fiber can be confirmed by observation with an electron microscope.
  • the fiber length distribution (%) of the contained fibers with a length load of 1.2 mm to 2.0 mm is 16% or more (preferably 19% or more), and the fiber length of a length load of 1.2 mm to 3.2 mm It is more preferable to use at least one slurry having a distribution (%) of 30% or more (preferably 35% or more).
  • the length-weighted fiber length distribution of fibers contained in the slurry can be measured, for example, by an optical measurement method (JAPAN TAPPI Paper Pulp Test Method No. 52 (Pulp and Paper-Fiber Length Test Method-Optical Automatic measurement method) or JIS P 8226 (pulp-fiber length measurement method by optical automatic analysis method-Part 1: Polarization method), JIS P 8226-2 (pulp-fiber length measurement method by optical automatic analysis method-part 1 2 part: see non-polarization method)).
  • JAPAN TAPPI Paper Pulp Test Method No. 52 Pulp and Paper-Fiber Length Test Method-Optical Automatic measurement method
  • JIS P 8226 pulp-fiber length measurement method by optical automatic analysis method-Part 1: Polarization method
  • JIS P 8226-2 pulse-fiber length measurement method by optical automatic analysis method-part 1 2 part: see non-polarization method
  • the length-weighted average fiber length (length-weighted mean length) of the fibers contained in the slurry used in the composite fiber production step is 1.2 mm or more and 1.5 mm or less.
  • the fibers constituting the composite fiber have the above-mentioned length-weighted average fiber length, it is possible to suppress the breaking of paper when continuously making a fiber sheet highly blended with a functional inorganic substance.
  • fibers having a length-weighted average fiber length of 1.0 mm or more and 2.0 mm or less are not limited to the total amount of fibers to be subjected to the synthesis of the composite fiber. It can be prepared by mixing 60% by weight or more.
  • the “length weighted average fiber length” can be measured, for example, using a known Metso Fractionater (manufactured by Metso).
  • the fiber group A it is preferable to use softwood kraft pulp because the fiber length is long, which is advantageous for improving the strength.
  • the length-weighted average fiber length of the fiber group A may be 1.0 mm or more and 2.0 mm or less, preferably 1.2 mm or more and 1.6 mm or less, more preferably 1.4 mm or more, 1 .6 mm or less.
  • the strength of the sheet obtained by the length weighted average fiber length being 1.2 mm or more is improved.
  • the gap unevenness of the sheet can be suppressed by being 1.6 mm or less.
  • Fibers having a length-weighted average fiber length of 1.0 mm or more and 2.0 mm or less Preferably, it may be 100% by weight.
  • fibers having a length-weighted average fiber length satisfying the above range include known softwood bleached kraft pulp (NBKP), softwood non-bleached kraft pulp (NUKP), thermomechanical pulp (TMP) and the like.
  • the length-weighted average fiber length of the fibers mixed with the fiber group A is not particularly limited.
  • the fiber group B may have a length-weighted average fiber length of, for example, less than 1.0 mm (preferably, 0.6 mm or more and less than 1.0 mm), and more than 2.0 mm (preferably May be greater than 2.0 mm and less than or equal to 3.2 mm), or may be greater than or equal to 1.0 mm and less than or equal to 2.0 mm.
  • Examples of cellulose fibers having such a length-weighted average fiber length include known hardwood bleached kraft pulp (LBKP), mechanical pulp (GP), deinked pulp (DIP), unbeaten pulp and the like. be able to.
  • the amount of fibers to be provided to the synthesis of the composite fibers in the composite fiber production step is preferably such that 15% or more of the surface of the fibers is covered with the inorganic particles.
  • the weight ratio of fiber to inorganic particles is preferably 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 may be used.
  • the fibers used for the synthesis of the composite fiber may be of any freeness, but 600 mL or less may be suitably used.
  • the length load of the fibers contained in the composite fiber production step is in the above-mentioned range, it is possible to further suppress the paper breaking when continuously making a fiber having a freeness of 600 mL or less. That is, when the treatment for increasing the fiber surface area such as beating is performed to improve the strength and specific surface area of the composite fiber sheet, the freeness becomes low, but the fiber subjected to such treatment can also be suitably used.
  • the lower limit value of the freeness of fibers is more preferably 50 mL or more, and still more preferably 100 mL or more. When the freeness of fibers is 200 mL or more, the operability of continuous papermaking is good.
  • the sheet forming step is a step of forming a sheet by making a composite fiber-containing slurry containing the composite fiber and a slurry for forming a sheet of the other layer.
  • the basis weight of the composite fiber sheet generated in the sheet forming step can be appropriately adjusted according to the purpose.
  • the basis weight of the composite fiber sheet can be adjusted to, for example, 15 g / m 2 or more and 800 g / m 2 or less, preferably 30 g / m 2 or more and 600 g / m 2 or less.
  • the composite fiber-containing slurry and the slurry for forming a sheet of another layer are subjected to a continuous paper machine, and papermaking is continuously performed so that sheets derived from each slurry are laminated.
  • a continuous paper machine it is not necessary to apply or laminate a functional material or sheet to a base sheet as in the prior art, and it is a multilayer having functionality more easily. Can produce sheets.
  • the continuous paper machine is not particularly limited, and a known paper machine (paper making machine) can be selected.
  • a fourdrinier paper machine for example, a fourdrinier paper machine, a cylinder paper machine, a long mesh / tilted combination paper machine, a gap former, a hybrid former, a multi-layered paper machine, a known paper making machine combining these paper making systems, etc. may be mentioned.
  • a Fourdrinier paper machine can be suitably employed.
  • a cylinder paper machine can be suitably adopted.
  • a cylinder paper machine is suitable for the production of composite fiber sheets having a high basis weight.
  • the cylinder paper machine has the advantage that the equipment is compact as compared to a fourdrinier paper machine.
  • a Fourdrinier paper machine has the advantage of being capable of high-speed papermaking as compared to a cylinder paper machine.
  • the press line pressure in the paper machine and the calendar line pressure in the case of calendering described later can be determined within a range that does not affect the operability 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 application.
  • the paper making speed in the sheet forming process is not particularly limited.
  • the paper making speed can be appropriately set according to the characteristics of the paper machine to be used, the basis weight of the sheet to be made, and the like. For example, when using a Fourdrinier paper machine, the paper making speed can be set to 1 m / min or more and 1500 m / min or less. Further, for example, when using a cylinder paper machine, the paper making speed can be 10 m / min or more and 300 m / min or less.
  • composite fiber containing slurry Composite fiber containing slurry
  • stock slurry Composite fiber containing slurry
  • the composite fibers contained in the composite fiber-containing slurry (referred to as “stock slurry” in the examples described later) used in the sheet forming step may be only one type, and may be a mixture of two or more types. It may be
  • Materials other than composite fibers may be further added to the composite fiber-containing slurry as long as papermaking is not hindered. Substances other than composite fibers are specifically described below.
  • the composite fiber-containing slurry may contain fibers which do not form the above-described composite fibers. It is preferable that the fibers not composited have a length-weighted average fiber length of 1.0 mm or more and 2.0 mm or less.
  • the paper strength of the composite fiber sheet can be improved by the composite fiber-containing slurry further including uncomposited fibers having a length-weighted average fiber length in the above range.
  • a retention agent may be added to the composite fiber-containing slurry in order to promote the retention of the filler to the fiber and to improve the retention of the filler and the fiber.
  • cationic or anionic, amphoteric polyacrylamide based materials can be used as a retention agent.
  • a retention system called a so-called dual polymer in which at least one or more cationic or anionic polymers are used in combination, and at least one or more anionic bentonite, colloidal silica, polysilicic acid,
  • the polyacrylamide-based material used alone or in combination has a weight average molecular weight of 2,000,000 Dalton or more according to the intrinsic viscosity method, good retention can be obtained, preferably 5,000,000 Dalton or more, and more preferably In the case of the acrylamide-based material having a viscosity of at least 10 million daltons and less than 30 million daltons, a very high yield can be obtained.
  • the form of the polyacrylamide based material may be an emulsion type or a solution type.
  • the specific composition is not particularly limited as long as it contains an acrylamide monomer unit as a structural unit in the substance, but, for example, a copolymer of a quaternary ammonium salt of acrylic acid ester and acrylamide, or acrylamide And quaternized ammonium salt after copolymerization with acrylic acid ester.
  • the cationic charge density of the cationic polyacrylamide based material is not particularly limited.
  • the retention agent is preferably in an amount of 0.001% to 0.1% by weight, more preferably 0.005% to 0.05% by weight, based on the total weight of fibers in the composite fiber-containing slurry. It can be added.
  • the composite fiber-containing slurry may further contain inorganic particles not complexed with fibers.
  • inorganic particles are distinguished from each other in that they do not bind to cellulose fibers by hydrogen bonding or the like as the inorganic particles constituting composite fibers, but are mixed with the fibers.
  • the type of inorganic particles (hereinafter referred to as "non-complexed inorganic particles") not complexed with fibers may be different from or the same as the inorganic particles constituting the composite fiber.
  • the non-complexed inorganic particles may have the same or similar function as the inorganic particles constituting the composite fiber, or may have different functions.
  • a composite fiber sheet having both functions can be manufactured by adding non-complexed inorganic particles which are different in kind from the inorganic particles constituting the composite fiber and have different functions.
  • the function can be further improved by adding the same type of externally added inorganic particles as the inorganic particles constituting the composite fiber or non-complexed inorganic particles different in type but having the same or similar function. it can.
  • the type of non-complexed inorganic particles may be appropriately selected according to the purpose.
  • the description of the inorganic particles constituting the above-mentioned composite fiber can be applied correspondingly. It is also possible to select particles generally called inorganic fillers.
  • the inorganic filler in addition to the above-mentioned inorganic particles, metal simple substance, clay, bentonite, diatomaceous earth, clay (kaolin, calcined kaolin, delami kaolin), talc, inorganic filler which regenerates and utilizes ash obtained from the deinking step
  • regenerate are mentioned. These may be used alone or in combination of two or more.
  • the weight ratio of the fibers in the conjugate fiber-containing slurry to the non-complexed inorganic particles may be set appropriately, and for example, preferably 99/1 to 70/30. Some may be effective with small additions, while others may require large additions depending on the application. In addition, when the addition amount is 30% or less, the yield is excellent.
  • Organic particles are particles of an organic compound.
  • organic flame retardant materials phosphoric acid type, boron type etc.
  • urea-formalin resin polystyrene resin, phenol resin, micro hollow particles, acrylamide composite fiber, wood Substances of origin (fine fibers, microfibril fibers, powder kenaf), modified insolubilized starch for improving printability, ungelatinized starch, latex and the like can be mentioned. These may be used alone or in combination of two or more.
  • the weight ratio of fibers to organic particles in the composite fiber-containing slurry may be set appropriately, and for example, preferably 99/1 to 70/30.
  • the addition amount of the organic particles may be set appropriately, and for example, preferably 99/1 to 70/30.
  • the addition amount of the organic particles may be set to 30% or less, a good yield can be obtained.
  • paper strength agent can be added to the composite fiber-containing slurry. Thereby, the strength of the composite fiber sheet can be improved.
  • paper strength agents include urea formaldehyde resin, melamine formaldehyde resin, polyamide, polyamine, epichlorohydrin resin, vegetable gum, latex, polyethylene imine, glyoxal, gum, mannogalactan polyethylene imine, polyacrylamide resin, polyvinyl amine And resins such as polyvinyl alcohol; composite polymers or copolymers consisting of two or more selected from the above resins; starch and modified starch; carboxymethyl cellulose, guar gum, urea resin and the like.
  • the addition amount of the paper strength agent is not particularly limited.
  • Polymeric polymers and inorganic substances can also be added to promote the fixing of the filler to the fiber and to improve the filler and the yield of the fiber.
  • polyethyleneimine and modified polyethyleneimine containing tertiary and / or quaternary ammonium groups as a coagulant polyalkyleneimine, dicyandiamide polymer, polyamine, polyamine / epichlorohydrin polymer, and dialkyldiallyl quaternary ammonium monomer
  • dialkyl Aminoalkyl acrylate, dialkylaminoalkyl methacrylate, dialkylaminoalkyl acrylamide and polymer of dialkylaminoalkyl methacrylamide and acrylamide polymer consisting of monoamines and epihalohydrin, polymer having polyvinylamine and vinylamine moiety, and mixtures thereof
  • inorganic particles such as drainage improver, internal sizing agent, pH adjuster, antifoamer, pitch control agent, slime control agent, bulking agent, calcium carbonate, kaolin, talc, silica Filler) etc.
  • the amount of each additive used is not particularly limited.
  • the slurry for forming the sheet of another layer may be appropriately prepared depending on the application of the multilayer sheet and the like.
  • the slurry for forming a sheet of another layer is adjusted in type and / or content of inorganic particles so as to have different properties from the sheet of a certain layer, and You may use the composite fiber containing slurry obtained by doing.
  • seat of another layer may be what added conventionally well-known fillers, such as the inorganic particle previously synthesize
  • the inorganic particle composite fiber sheet which consists of a multilayer sheet in which two or more composite fiber sheets were laminated
  • a plurality of composite fiber sheets may be stacked to form a laminate.
  • the method for producing the multilayer sheet is not particularly limited.
  • a multi-layer sheet can be produced by using a known long screen / gradient combination paper machine to composite a composite fiber sheet with a sheet containing no composite fiber. Thereby, since the paper strength of a composite fiber sheet can be improved, a composite fiber sheet can be manufactured without being cut by a continuous paper machine.
  • the specific tear strength of the multilayer sheet is 3.0 mN / (g / m 2 ) or more, 15.0 mN / Multilayer sheets of (g / m 2 ) or less can be produced by a continuous paper machine without breaking.
  • the specific tear strength is further enhanced.
  • a multilayer sheet can be produced without being cut by a continuous paper machine with a stock yield of 70% or more.
  • an inorganic particle composite fiber sheet can be manufactured by 60% or more of ash fraction retention, without being cut by a continuous paper machine.
  • the present invention includes, but is not limited to, the following inventions.
  • the sheet containing the composite fiber of the fiber and the inorganic particle is contained in two or more layers, and the type of inorganic particle contained in one layer is different from the type of inorganic particle contained in at least one other layer ((1) Or the multilayer sheet described in (2).
  • Example 1 Production of Multilayer Sheet Containing Barium Sulfate Composite Fiber Sheet (1) Synthesis of Composite Fiber of Barium Sulfate and Cellulose Fiber Sheet
  • a single disc refiner (0: 100 weight ratio of hardwood bleached kraft pulp (LBKP) and softwood bleached kraft pulp (NBKP) is included.
  • the pulp fiber prepared to 290 mL of Canadian standard freeness (CSF) using SDR) was used.
  • the fiber length distribution of the cellulose fibers used in the composite in Example 1 for the length load of 1.2 mm or more and 2.0 mm or less is 22%, and the fiber length distribution for the length load of 1.2 mm or more and 3.2 mm or less is 39 %, And the total length weighted average fiber length is 1.4 mm.
  • the above-mentioned "hardwood bleached kraft pulp” is abbreviated as "LBKP”.
  • “the softwood bleached kraft pulp” is abbreviated and described as "NBKP.” Both LBKP and NBKP were manufactured by Nippon Paper Industries.
  • the above-mentioned "Canada standard freeness" is abbreviated as "CSF”.
  • Pulp slurry Pulp fiber concentration: 1.8% by weight, pulp solid content 36 kg
  • barium hydroxide containing the pulp fibers in a container machine chest, volume: 4 m 3
  • octahydrate Nippon Chemical Industry Co., Ltd., 147 kg
  • a sulfuric acid band Wako Pure Chemical Industries, 198 kg
  • stirring was continued as it is for 60 minutes to obtain a slurry of the composite fiber of Example 1.
  • Example 1 since a sulfuric acid band is used as a raw material for synthesizing barium sulfate, not only barium sulfate but also an aluminum compound such as aluminum hydroxide is synthesized. Therefore, in Example 1, a composite fiber of an aluminum compound such as barium sulfate and aluminum hydroxide and a cellulose fiber is synthesized.
  • the surface of the obtained conjugate fiber was observed using an electron microscope. As a result of observation, it was observed that the fiber surface was covered with the inorganic substance by 15% or more, and it was observed that it was self-fixed. Most of the inorganic particles fixed to the fibers were plate-like, and those with small size were observed as amorphous particles. Moreover, the average primary particle diameter of the inorganic particle estimated as a result of observation was 1 micrometer or less.
  • the weight ratio (ash content) is obtained by suction-filtering the composite fiber slurry (3 g in terms of solid content) using filter paper, then drying the residue in an oven (105 ° C., 2 hours), and further organic matter at 525 ° C. It burns and it computed from the weight before and behind combustion.
  • the lead equivalent of each sample was determined by preparing an attenuation factor curve from the standard lead version.
  • the attenuation factor curve was created by quadratic interpolation from the attenuation factors of four standard lead plates with different thicknesses.
  • Example 2 Production of Multilayer Sheet Containing Hydrotalcite Composite Fiber Sheet (1) Synthesis of Composite Fiber of Hydrotalcite and Cellulose Fiber (1-1) Preparation of Alkaline Solution and Acid Solution A solution for synthesizing hydrotalcite (HT) was prepared. A mixed aqueous solution of Na 2 CO 3 (Wako Pure Chemical Industries, Ltd.) and NaOH (Wako Pure Chemical Industries, Ltd.) was prepared as an alkaline solution (solution A). In addition, a mixed aqueous solution of ZnCl 2 (Wako Pure Chemical Industries, Ltd.) and AlCl 3 (Wako Pure Chemical Industries, Ltd.) was prepared as an acid solution (solution B).
  • Pulp fibers were added to the alkaline solution to prepare an aqueous suspension containing pulp fibers (pulp fiber concentration: 4.0% by weight, pH: 13).
  • This aqueous suspension (pulp solid content 80 kg) is placed in a reaction vessel (machine chest, volume: 4 m 3 ), and while stirring the aqueous suspension, an acid solution (Zn-based) is dropped to obtain hydrotalcite fine particles and Composite fiber with fiber (Zn 6 Al 2 (OH) 16 CO 3 .4H 2 O) was synthesized.
  • the reaction temperature was 60 ° C.
  • the dropping rate was 1.5 kg / min
  • the dropping was stopped when the pH of the reaction solution reached about 6.5.
  • the reaction solution was stirred for 60 minutes and washed with an equal amount of water to remove salts.
  • the fiber surface was covered by 15% or more, and the average primary particle diameter was 1 ⁇ m or less.
  • the weight ratio of fiber to inorganic particles in the obtained composite fiber was 50: 50 (ash content: 50%).
  • the antibacterial properties of the multilayer sheet produced in Experiment 2 were evaluated.
  • the antibacterial test was carried out according to the bacterial fluid absorption method (a quantitative test method in which a test inoculum is directly inoculated on a test piece) defined in JIS L 1902.
  • Two types of Staphylococcus aureus (Staphylococcus aureus NBRC 12732) and E. coli (Escherichia coil NBRC 3301) were used as the test bacterial species, and the viable cell count after 18 hours of culture was measured by the pour plan culture method. Standard cotton cloth was used as a standard.
  • the test procedure is shown below. 1.
  • test piece 0.4 g of a test piece is placed in a vial, and 0.2 mL of the test solution (containing 0.05% surfactant (Tween 80)) is dropped, and then the vial is capped. 2. The vials are incubated at 37 ° C. for 18 hours. 3. 20 mL of the washout solution is added to wash out the test bacteria from the test piece, and the number of viable bacteria in the washout solution is measured by the pour plate culture method or the luminescence measurement method. 4.
  • the antibacterial activity value is calculated according to the following formula. The antibacterial activity value of 2.0 or more means that the kill rate of bacteria is 99% or more.
  • Antibacterial activity value ⁇ log (control sample, viable count after culture)-log (control sample, viable count immediately after inoculation) ⁇ - ⁇ log (test sample, viable count after culture)-log (test sample, viable immediately after inoculation) number) ⁇ (5-4) Result When the antimicrobial activity value was 2.0 or more, it was evaluated as ⁇ . The results are shown in Table 1. As shown in Table 1, the multilayer sheet of the present example exhibited extremely high antibacterial properties to the target bacterial species.
  • Example 3 Production of Multilayer Sheet Containing Hydrotalcite Composite Fiber Sheet and Magnesium Carbonate Composite Fiber Sheet (1) Synthesis of Composite Fiber of Hydrotalcite and Cellulose Fiber The same operation as in Example 2 was performed to synthesize.
  • An aqueous suspension 400 L was prepared by adding 8.0 kg of magnesium hydroxide (Ube Materials, UD 653) and 8.0 kg of the pulp fibers into water. As shown in FIG. 2, this aqueous suspension is placed in a cavitation apparatus (500 L volume), carbon dioxide gas is blown into the reaction vessel while circulating the reaction solution, and a composite of magnesium carbonate fine particles and fibers is formed by carbon dioxide gas method. The fibers were synthesized.
  • the reaction initiation temperature was about 40 ° C.
  • carbon dioxide gas was supplied from a commercial liquefied gas, and the amount of carbon dioxide gas blown was 20 L / min.
  • the pH of the reaction solution reached about 7.4, the introduction of CO 2 was stopped (the pH before reaction was 10.3), and then the generation of cavitation and the slurry circulation in the apparatus were continued for 30 minutes. A slurry of composite fibers was obtained.
  • cavitation bubbles were generated in the reaction vessel by circulating the reaction solution and injecting it into the reaction vessel as shown in FIG. Specifically, the reaction solution was jetted at high pressure through a nozzle (nozzle diameter: 1.5 mm) to generate cavitation bubbles, but the jet velocity was about 70 m / s, and the inlet pressure (upstream pressure) was The outlet pressure (downstream pressure) was 7 MPa and 0.3 MPa.
  • the fiber surface was covered by 15% or more, and the average primary particle diameter was 1 ⁇ m or less.
  • the weight ratio of fiber to inorganic particles in the obtained composite fiber was 50: 50 (ash content: 50%).
  • the board cut to a predetermined size (20 cm ⁇ 30 cm) was dried at 50 ° C. for 48 hours, and then left in a desiccator containing silica gel for drying for 24 hours to be a sample of a burning test (heating test).
  • the sample is attached to a support frame (inner size of the frame 16 cm ⁇ 25 cm) and attached to a heating test device, and after ignited by a gas burner, the sample is heated for 2 minutes to measure the carbonized area, afterflame time and retention time did.
  • a 45 ° flammability tester manufactured by Suga Test Instruments Co., Ltd., FL-45M
  • a Meckel burner heat 160 mm, inner diameter 20 mm
  • the fuel used was liquefied petroleum gas No. 5 (mainly containing butane and butylene, JIS K 2240), and was adjusted to have a flame length of 65 mm with no sample attached.
  • After-flame time The time for which the test body burns from the end of heating and keeps on burning was measured.
  • ⁇ Remaining dust A state in which flameless combustion has occurred since the end of heating.
  • Carbonized long area The maximum length and the maximum width were measured for the carbonized portion of the heating surface of the test body (carbonized to obviously change the strength), and they were calculated by multiplying them.
  • Comparative Example 1 Production of a Multilayer Sheet Composed of Only a Fiber Sheet Containing No Inorganic Particles
  • a stock slurry was prepared in the same manner as in Example 1 except that barium sulfate was not synthesized.
  • the same operation as in Example 1 was carried out using the stock slurry as a slurry for the first layer and the second layer to produce a two-layer sheet (basis weight 180 g / m 2 ). It has a thickness of 281 ⁇ m and contains no ash.
  • the radiation shielding property, the deodorizing property, the antibacterial property and the flame retardant property were all inferior to the examples having the respective functions.
  • One aspect of the present invention can be suitably used in the papermaking field.

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  • Paper (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une feuille multicouche qui peut être facilement produite en stratifiant des feuilles possédant d'autres fonctions, sur une feuille donnée, en utilisant une feuille possédant un rendement élevé et contenant des particules inorganiques. Selon un mode de réalisation de la présente invention, la feuille multicouche possède au moins deux couches de feuilles stratifiées contenant des fibres, au moins une couche de feuilles contenant des fibres, et des fibres composites de particules inorganiques, et affichant des propriétés différentes de celles des autres couches de feuilles.
PCT/JP2018/033964 2017-09-27 2018-09-13 Feuille multicouche et son procédé de production WO2019065270A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021045198A1 (fr) * 2019-09-06 2021-03-11 日本製紙株式会社 Fibre composite comprenant une fibre de cellulose et des particules inorganiques, et son procédé de fabrication

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59157397A (ja) * 1983-02-26 1984-09-06 新富士製紙株式会社 石膏ボ−ド用板紙
JPH01321996A (ja) * 1988-06-20 1989-12-27 Rengo Co Ltd 繊維状ウエブの湿式成形装置
JPH08258400A (ja) * 1995-03-24 1996-10-08 Mitsubishi Paper Mills Ltd インクジェット記録用紙
JP2011001675A (ja) * 2009-05-20 2011-01-06 Oji Paper Co Ltd 葉書の製造方法
WO2013140844A1 (fr) * 2012-03-22 2013-09-26 日本製紙株式会社 Carton blanc et matière imprimée, boîte imprimée ou contenant d'emballage, chacun produit avec celui-ci
WO2017057154A1 (fr) * 2015-09-30 2017-04-06 日本製紙株式会社 Matériau composite en fibres de cellulose et en particules inorganiques

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59157397A (ja) * 1983-02-26 1984-09-06 新富士製紙株式会社 石膏ボ−ド用板紙
JPH01321996A (ja) * 1988-06-20 1989-12-27 Rengo Co Ltd 繊維状ウエブの湿式成形装置
JPH08258400A (ja) * 1995-03-24 1996-10-08 Mitsubishi Paper Mills Ltd インクジェット記録用紙
JP2011001675A (ja) * 2009-05-20 2011-01-06 Oji Paper Co Ltd 葉書の製造方法
WO2013140844A1 (fr) * 2012-03-22 2013-09-26 日本製紙株式会社 Carton blanc et matière imprimée, boîte imprimée ou contenant d'emballage, chacun produit avec celui-ci
WO2017057154A1 (fr) * 2015-09-30 2017-04-06 日本製紙株式会社 Matériau composite en fibres de cellulose et en particules inorganiques

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021045198A1 (fr) * 2019-09-06 2021-03-11 日本製紙株式会社 Fibre composite comprenant une fibre de cellulose et des particules inorganiques, et son procédé de fabrication
JPWO2021045198A1 (ja) * 2019-09-06 2021-09-27 日本製紙株式会社 セルロース繊維と無機粒子の複合繊維およびその製造方法
JP7123178B2 (ja) 2019-09-06 2022-08-22 日本製紙株式会社 セルロース繊維と無機粒子の複合繊維およびその製造方法

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