[go: up one dir, main page]

WO2025115763A1 - Matériau ignifuge, et feuille ignifuge - Google Patents

Matériau ignifuge, et feuille ignifuge Download PDF

Info

Publication number
WO2025115763A1
WO2025115763A1 PCT/JP2024/041364 JP2024041364W WO2025115763A1 WO 2025115763 A1 WO2025115763 A1 WO 2025115763A1 JP 2024041364 W JP2024041364 W JP 2024041364W WO 2025115763 A1 WO2025115763 A1 WO 2025115763A1
Authority
WO
WIPO (PCT)
Prior art keywords
pulp
flame
sheet
anion
retardant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2024/041364
Other languages
English (en)
Japanese (ja)
Inventor
洋介 後居
圭樹 伊藤
継之 齋藤
秀次 藤澤
瞬 石岡
昊果 張
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Tokyo NUC
DKS Co Ltd
Original Assignee
University of Tokyo NUC
DKS Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Tokyo NUC, DKS Co Ltd filed Critical University of Tokyo NUC
Publication of WO2025115763A1 publication Critical patent/WO2025115763A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00—Preparation of cellulose ethers
    • C08B11/02—Alkyl or cycloalkyl ethers
    • C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
    • C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
    • C08B11/12—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C08B15/04—Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B5/00—Preparation of cellulose esters of inorganic acids, e.g. phosphates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B5/00—Preparation of cellulose esters of inorganic acids, e.g. phosphates
    • C08B5/14—Cellulose sulfate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/14—Macromolecular materials
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • 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
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/20—Chemically or biochemically modified fibres

Definitions

  • the present invention relates to a flame-retardant material and a flame-retardant sheet containing anionically modified pulp.
  • Pulp is not inherently flame retardant, and neither is paper made from pulp. To make it flame retardant, flame retardants such as inorganic compounds are added, but they must be added in large quantities and are not easy to disperse evenly.
  • Patent Document 1 discloses a flame-retardant molded product containing composite fibers, such as cellulose fibers, whose fiber surfaces are coated with inorganic particles, and a water-insoluble flame retardant, and discloses that the molded product has a sheet shape, and that the composite fiber is prepared by synthesizing inorganic particles in a liquid containing the fibers.
  • Patent Document 1 also discloses anion-modified cellulose fibers, such as TEMPO-oxidized CNF, as the fiber, but does not disclose that metal salts of anion-modified pulp have flame retardant properties.
  • An embodiment of the present invention aims to provide a novel flame-retardant material and a flame-retardant sheet that contain anionically modified pulp.
  • the inventors discovered that pulp can be made flame retardant by introducing anionic groups into the pulp and converting the anionic groups into metal salts, and came up with the idea of using metal salts of such anion-modified pulp to make flame retardant materials and flame retardant sheets.
  • the present invention includes the following embodiments.
  • a flame-retardant material comprising an anion-modified pulp in which a counter ion of an anionic group contains a metal ion, the anion-modified pulp having an amount of anionic groups, measured after all of the anionic groups are in an acid form, of 1.1 to 3.0 mmol/g.
  • a flame-retardant sheet comprising an anion-modified pulp in which a counter ion of an anionic group contains a metal ion, the anion-modified pulp having an amount of anionic groups, measured after all of the anionic groups are converted to an acid form, of 1.1 to 3.0 mmol/g.
  • a novel flame-retardant material and a flame-retardant sheet containing anion-modified pulp can be provided.
  • the flame-retardant material according to the present embodiment includes anion-modified pulp in which the counter ion of the anionic group contains a metal ion.
  • anion-modified pulp metal ions can be efficiently introduced into the anionic group, and the pulp can be made flame-retardant. Therefore, it can be used as a material for imparting flame retardancy.
  • metal ions for example, when the pulp is made into a sheet, strength such as tensile strength can be increased, and therefore both strength and flame retardancy can be achieved.
  • Anionically modified pulp is pulp to which anionic groups have been introduced, and is obtained by chemically modifying unmodified pulp.
  • Pulp refers to cellulose fibers extracted by mechanically and/or chemically treating plants such as wood. It is preferable that the anionic groups are introduced at least to the fiber surface of the pulp.
  • plant-derived pulps include unbleached softwood kraft pulp (NUKP), bleached softwood kraft pulp (NBKP), unbleached hardwood kraft pulp (LUKP), bleached hardwood kraft pulp (LBKP), unbleached softwood sulfite pulp (NUSP), bleached softwood sulfite pulp (NBSP), thermomechanical pulp (TMP), recycled pulp, and waste paper pulp. These may be used alone or in combination of two or more.
  • the anionic group may be, for example, at least one selected from the group consisting of a carboxy group, a phosphate group, a sulfate group, a sulfonate group, a nitrate group, and a borate group. Of these, at least one selected from the group consisting of a carboxy group, a phosphate group, and a sulfate group is preferred.
  • These anionic groups may be directly or indirectly bonded to glucose units, which are structural units of cellulose molecules. When indirectly bonded, for example, an alkylene group having 1 to 4 carbon atoms may be present between the glucose unit and the anionic group.
  • One or more anionic groups may be bonded to all glucose units constituting the cellulose molecule, or one or more anionic groups may be bonded to some of the glucose units constituting the cellulose molecule.
  • the anionic group of the anion-modified pulp is preferably a carboxy group.
  • the carboxy group has a greater effect of improving the strength of the pulp when it is used to make a sheet than other anionic groups.
  • examples of anion-modified pulp having a carboxy group include oxidized cellulose fibers obtained by oxidizing the hydroxyl groups of glucose units in cellulose molecules, and carboxymethylated cellulose fibers obtained by carboxymethylating the hydroxyl groups of glucose units in cellulose molecules.
  • examples of oxidized cellulose fibers include those in which the hydroxyl group at the C6 position of the glucose unit in the cellulose molecule is selectively oxidized to a carboxy group.
  • Oxidized cellulose fibers are obtained by oxidizing natural cellulose such as wood pulp using a co-oxidizing agent in the presence of an N-oxyl compound.
  • N-oxyl compound a compound having a nitroxy radical that is generally used as an oxidation catalyst is used, for example, a piperidine nitroxyoxy radical, and in particular, 2,2,6,6-tetramethylpiperidinooxy radical (TEMPO) or 4-acetamide-TEMPO is preferred.
  • TEMPO 2,2,6,6-tetramethylpiperidinooxy radical
  • 4-acetamide-TEMPO is preferred.
  • the anion-modified cellulose fiber according to a preferred embodiment is a TEMPO-oxidized cellulose fiber oxidized using TEMPO.
  • the anion-modified pulp has an amount of anionic groups of 1.1 to 3.0 mmol/g, measured after all the anionic groups are in the acid form.
  • the amount of anionic groups is preferably 1.3 to 2.8 mmol/g, more preferably 1.5 to 2.6 mmol/g, and even more preferably 1.7 to 2.5 mmol/g. Since the anion-modified pulp according to this embodiment is a metal salt-type anion-modified pulp, all the anionic groups are converted to the acid form before the amount of anionic groups is measured.
  • the amount of anionic groups is the amount of substance (mmol) of anionic groups per dry mass of the acid-type anion-modified pulp, and can be measured by a known method, and in detail, can be measured by the method described in the Examples section.
  • dry mass refers to the mass after drying at 140°C until the mass change rate per minute is 0.05% or less.
  • the anion-modified pulp used has a metal ion as a counter ion of the anionic group. That is, a metal ion is bonded to the anionic group to form a metal salt.
  • the counter ions of all the anionic groups are metal ions, but the counter ions may be other than metal ions.
  • the anionic group may contain an onium salt together with the metal salt, and may not all be salt-type, and may contain an acid type (the counter ion is H + , also called H type.
  • H + also called H type.
  • the amount of the metal salt introduced is, for example, preferably 50 mol % or more of the anionic group, more preferably 80 mol % or more, more preferably 90 mol % or more, and even more preferably 100 mol %.
  • the amount of the metal salt introduced is the ratio of the anionic group forming the metal salt to 100 mol % of the anionic group, and is calculated from the amount of the anionic group and the metal content measured by an ICP emission spectrometer.
  • the above metal ions include, for example, monovalent metal ions such as sodium ions, lithium ions, and potassium ions, divalent metal ions such as magnesium ions and calcium ions, and trivalent metal ions such as aluminum ions. These may be used alone or in combination of two or more.
  • the metal ions may be monovalent metal ions alone, or polyvalent metal ions such as magnesium ions, calcium ions, or aluminum ions alone, or a combination of monovalent and polyvalent metal ions.
  • Combined use means that the anionic groups in the anion-modified pulp include anionic groups bonded to monovalent metal ions and anionic groups bonded to polyvalent metal ions.
  • the metal ions preferably include polyvalent metal ions from the viewpoint of flame retardancy and strength. That is, the metal ions as counter ions may be polyvalent metal ions alone, or may be a combination of polyvalent metal ions and monovalent metal ions.
  • the ratio of polyvalent metal ions to 100 mol% of metal ions is not particularly limited, but is preferably 30 mol% or more, more preferably 50 mol% or more, even more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably 100 mol%.
  • the ratio of polyvalent metal ions is determined by measuring the content of various metals using an ICP emission spectrometer, and in detail, can be measured by the method described in the Examples section.
  • anionically modified pulp is obtained by chemically modifying unmodified pulp and is not defibrated. In this respect, it is distinguished from cellulose nanofibers, which are made by defibrating pulp.
  • the fiber diameter of anionically modified pulp is the same as that of untreated pulp, and although it differs depending on the raw material pulp, it is usually several tens of ⁇ m.
  • the number average fiber width of anionically modified pulp is preferably 5 to 100 ⁇ m, more preferably 10 to 60 ⁇ m, and may be 20 to 40 ⁇ m.
  • the number average fiber width of anionically modified pulp is measured as follows: an aqueous suspension of anionically modified pulp diluted to 0.01% by mass is photographed using an optical microscope, 10 images are taken, 25 fibers are selected from the images, the fiber widths (diameters) are measured, and the arithmetic mean is calculated.
  • the flame-retardant material according to this embodiment may consist of only the anion-modified pulp, or may contain additives as optional components together with the anion-modified pulp.
  • the amount of the anion-modified pulp in the flame-retardant material is not particularly limited, but is preferably 70% by mass or more, more preferably 80% by mass or more, more preferably 90% by mass or more, more preferably 95% by mass or more, and may be 100% by mass.
  • additives include colorants such as pigments and dyes, water-resistant agents, flame retardants, plasticizers, antioxidants, light stabilizers, fillers, and antistatic agents.
  • the flame-retardant material according to this embodiment does not require other flame retardants, and therefore, in one embodiment, the flame-retardant material does not contain other flame retardants.
  • the form of the flame-retardant material is not particularly limited, and may be, for example, fibrous.
  • Fibrous refers to something that has the form of fibers, and may be an aggregate of fibers, such as cotton, or a fiber sheet such as paper or nonwoven fabric.
  • the flame-retardant material according to this embodiment is used to impart flame retardancy.
  • the material can be made less flammable or the flames can be prevented from spreading, thereby imparting flame retardancy to the material.
  • a flame-retardant paper product when producing paper products such as paper, can be obtained by adding and mixing a flame-retardant material containing the anion-modified pulp with unmodified pulp and producing a paper product according to a normal method.
  • a flame-retardant resin product can be obtained by adding and mixing the flame-retardant material with a resin and producing a resin product according to a normal method.
  • Paper products are not particularly limited, and examples include architectural interior materials such as wallpaper, filters, honeycomb materials, and packaging materials.
  • the flame-retardant sheet according to this embodiment is a sheet containing anion-modified pulp in which the counter ions of the anionic groups contain metal ions, and the amount of anionic groups in the anion-modified pulp, measured after all the anionic groups are in the acid form, is 1.1 to 3.0 mmol/g. Details of the anion-modified pulp are as described above for the flame-retardant material, and will not be described here.
  • the flame-retardant sheet is a sheet used to impart flame retardancy, and can be used by layering it on the surface or inside of an object to be made flame-retardant (i.e., a target object) to impart flame retardancy to the object.
  • the flame-retardant sheet can be attached to the surface of the target object or sandwiched inside a laminate that is the target object. More specific uses include, for example, wallpaper and other architectural interior sheets, filters, honeycomb materials, and packaging materials.
  • sheet is a concept that encompasses "film.”
  • the flame-retardant sheet may be a sheet with a single layer structure consisting of a layer containing the anion-modified pulp, or a sheet with a laminate structure containing a layer containing the anion-modified pulp and another layer.
  • the thickness of the flame-retardant sheet is not particularly limited, and may be, for example, 0.001 to 50 mm, or 0.01 to 5 mm.
  • the flame-retardant sheet may consist only of the anion-modified pulp, or may contain additives as optional components in addition to the anion-modified pulp.
  • additives include colorants such as pigments and dyes, water-resistant agents, flame retardants, plasticizers, antioxidants, light stabilizers, fillers, and antistatic agents.
  • the flame-retardant sheet according to this embodiment does not require other flame retardants, and therefore, in one embodiment, the flame-retardant sheet does not contain other flame retardants.
  • the flame-retardant sheet may be a fiber sheet such as paper or nonwoven fabric.
  • a suspension containing anion-modified pulp may be used as a paper stock to make paper by papermaking.
  • Papermaking is a process in which the paper stock is dehydrated by filtration to form a sheet, which is then pressed and dried to make paper.
  • a known papermaking machine such as a Fourdrinier wet papermaking machine, a twin-wire papermaking machine, a Yankee papermaking machine, a cylinder papermaking machine, or a cylinder-short wire combination papermaking machine may be used.
  • a suspension containing anion-modified pulp may be filtered under reduced pressure to form a sheet, which is then dried and pressed to make a fiber sheet.
  • the method for preparing the anion-modified pulp is not particularly limited, but may be prepared, for example, by forming a sheet using a monovalent metal salt of the anion-modified pulp, and then immersing the sheet in an aqueous solution of the polyvalent metal salt to replace the monovalent metal ions with polyvalent metal ions.
  • the flame-retardant sheet may contain unmodified pulp together with the anion-modified pulp, or may be a composite sheet in which anion-modified pulp and unmodified pulp are combined.
  • a composite sheet may be prepared by using a suspension containing both anion-modified pulp and unmodified pulp as a paper stock, or by filtering a suspension containing both anion-modified pulp and unmodified pulp under reduced pressure in the production of the fiber sheet described above.
  • the ratio of anionically modified pulp to unmodified pulp is not particularly limited, and may be, for example, 10/90 to 90/10, 20/80 to 80/20, or 30/70 to 70/30 in mass ratio of anionically modified pulp/unmodified pulp.
  • a 50 mL aqueous suspension of an acid-type anion-modified pulp with a pulp concentration of 0.1% by mass was prepared, and the pH was adjusted to about 2.5 with a 0.1 mol/L aqueous hydrochloric acid solution. Next, a 0.05 mol/L aqueous sodium hydroxide solution was dropped into the aqueous suspension, and the electrical conductivity was measured until the pH reached about 11.
  • the amount of carboxyl groups was calculated according to the following formula from the amount of sodium hydroxide (V) consumed in the neutralization stage of the weak acid, where the change in electrical conductivity was gradual.
  • Carboxylic group amount (mmol/g) V (mL) x [0.05/mass of acid-type anion-modified pulp (g)]
  • the anion-modified pulp was diluted with ion-exchanged water to a content of 0.2% by mass, and the aqueous suspension was treated with an ion-exchange resin to obtain an acid-type anion-modified pulp.
  • the ion-exchange resin treatment was carried out by adding 1/10 by volume of a strongly acidic ion-exchange resin (Amberjet 1024; Organo Corporation, conditioned) to the aqueous suspension, shaking the suspension for 1 hour, and then pouring the suspension onto a mesh with an opening of 90 ⁇ m to separate the ion-exchange resin from the aqueous suspension.
  • a strongly acidic ion-exchange resin Amberjet 1024; Organo Corporation, conditioned
  • the alkali titration was carried out by adding 50 ⁇ L of 0.1 mol/L sodium hydroxide aqueous solution to the aqueous suspension after the ion-exchange resin treatment once every 30 seconds, while measuring the change in the electrical conductivity value of the aqueous suspension.
  • the amount of phosphate groups (mmol/g) was calculated by dividing the amount of alkali (mmol) required in the region corresponding to the first region of the measurement results by the solid content (g) in the aqueous suspension to be titrated.
  • a predetermined amount of acid-type anion-modified pulp was combusted, and the sulfur content in the combustion product was measured using a combustion ion chromatograph according to a method in accordance with IEC 62321, and calculated in terms of the amount of sulfate groups.
  • Sheets C1 to C9 of Examples 1 to 9 and sheets C11 to C13 and C15 of Comparative Examples 1 to 3 and 5 were cut into 5 cm length x 1 cm width to prepare test pieces.
  • the test pieces were fixed horizontally with clamps, and a gas burner flame was applied to the tip of the test pieces. Flame retardancy was evaluated according to the following criteria.
  • B The test piece self-extinguished over 60 seconds or more after the gas burner flame came into contact with the test piece.
  • C The entire test piece was burned.
  • Test pieces were prepared by cutting sheets C1 to C9 of Examples 1 to 9 and sheets C11 to C13 and C15 of Comparative Examples 1 to 3 and 5 to 6 cm length x 0.5 cm width. Using a tensile tester (EZ-SX, manufactured by Shimadzu Corporation), the test pieces were subjected to a tensile test under the conditions of a gripping distance of 3 cm, a tensile speed of 3 mm/min, 23°C, and 50% RH to determine the tensile strength (MPa). The tensile strength is the maximum tensile force recorded when the test piece is pulled until it breaks, divided by the cross-sectional area of the test piece before the test.
  • EZ-SX tensile tester
  • the pH of the slurry was then adjusted to 10 with a 24% by mass aqueous solution of sodium hydroxide, and sodium borohydride was added at 0.2 mmol/g relative to the cellulose fibers to initiate the reaction.
  • the reaction was allowed to proceed for 2 hours for reduction treatment.
  • 0.1 mol/L hydrochloric acid was added to adjust the pH to 2.0, and the pulp was purified by repeatedly filtering and washing with water to obtain an anion-modified pulp A1 in which the carboxyl group is in the acid form.
  • Example 1 (neutralization process) The anion-modified pulp A2 was diluted to 0.2% by mass with ion-exchanged water, and then neutralized with a 0.5 mol/L aqueous sodium hydroxide solution to a pH (25° C.) of 7.0, thereby obtaining a suspension B1 of anion-modified pulp having a Na salt type carboxy group.
  • the suspension B1 was filtered under reduced pressure through a nylon mesh filter with an opening of 59 ⁇ m to obtain a sheet-like wet deposit. After air drying at room temperature, the sheet was sandwiched between polyimide films and heated at 105° C. for 5 minutes at 0.4 MPa using a heat press device to obtain a sheet having Na salt-type carboxy groups. The sheet having Na salt-type carboxy groups was immersed in a 0.1 M aqueous aluminum chloride solution for 24 hours and then washed five times with purified water. After air drying, the sheet was sandwiched between polyimide films and heated at 105° C. for 5 minutes at 0.4 MPa using a heat press device to obtain a sheet C1 of Example 1 having a thickness of 100 ⁇ m, which is made of an anion-modified pulp having Al salt-type carboxy groups.
  • the unmodified softwood pulp was diluted to 0.2% by mass with ion-exchanged water and disintegrated for 10 minutes at 3000 rpm using a pulper to prepare a pulp suspension.
  • the pulp suspension was mixed with the suspension B1 of anion-modified pulp having a Na salt type carboxy group obtained in the neutralization step in a mass ratio of 50:50. This was filtered under reduced pressure using a nylon mesh filter with an opening of 59 ⁇ m to obtain a sheet-like wet deposit. After air drying at room temperature, the mixture was sandwiched between polyimide films and heated at 105° C.
  • Example 2 The neutralization step, the preparation of the sheet, and the preparation of the composite sheet were carried out in the same manner as in Example 1, except that the anion-modified pulp A1 was used, to obtain a sheet C2 and a composite sheet D2 of Example 2.
  • Example 3 The neutralization step, the preparation of the sheet, and the preparation of the composite sheet were carried out in the same manner as in Example 1, except that the anion-modified pulp A3 was used, to obtain a sheet C3 and a composite sheet D3 of Example 3.
  • Example 4 The neutralization process, sheet preparation, and composite sheet preparation were carried out in the same manner as in Example 2, except that in the preparation of the sheet and the preparation of the composite sheet, the aluminum chloride solution was immersed in 0.05 M aluminum chloride aqueous solution instead of 0.1 M aluminum chloride aqueous solution, to obtain sheet C4 and composite sheet D4 of Example 4.
  • Example 5 The neutralization process, sheet preparation, and composite sheet preparation were carried out in the same manner as in Example 2, except that the sheet preparation and composite sheet preparation were not immersed in a 0.1 M aluminum chloride aqueous solution, thereby obtaining sheet C5 and composite sheet D5 of Example 5.
  • Example 6 The neutralization process, sheet preparation, and composite sheet preparation were carried out in the same manner as in Example 2, except that in the preparation of the sheet and the preparation of the composite sheet, the sheet was immersed in a 0.1 M aqueous magnesium chloride solution instead of a 0.1 M aqueous aluminum chloride solution, to obtain sheet C6 and composite sheet D6 of Example 6.
  • Example 7 The neutralization process, sheet preparation, and composite sheet preparation were carried out in the same manner as in Example 2, except that in the preparation of the sheet and the preparation of the composite sheet, the sheet was immersed in a 0.1 M calcium chloride aqueous solution instead of a 0.1 M aluminum chloride aqueous solution, to obtain sheet C7 and composite sheet D7 of Example 7.
  • Example 8 The neutralization step, the preparation of the sheet, and the preparation of the composite sheet were carried out in the same manner as in Example 1, except that the anion-modified pulp A5 was used, to obtain the sheet C8 and the composite sheet D8 of Example 8.
  • Example 9 The neutralization step, the preparation of the sheet, and the preparation of the composite sheet were carried out in the same manner as in Example 1, except that the anion-modified pulp A6 was used, to obtain a sheet C9 and a composite sheet D9 of Example 9.
  • Comparative Example 1 The unmodified softwood pulp was diluted to 0.2% by mass with ion-exchanged water, and then disintegrated for 10 minutes at 3000 rpm using a pulper to prepare a pulp suspension. The resulting suspension was filtered under reduced pressure using a nylon mesh filter with a mesh size of 59 ⁇ m to obtain a sheet-like wet deposit. After air drying at room temperature, the sheet was sandwiched between polyimide films and heated at 105° C. for 5 minutes at 0.4 MPa using a heat press device to obtain a sheet C11 of Comparative Example 1 having a thickness of 100 ⁇ m.
  • the suspension B12 was filtered under reduced pressure through a nylon mesh filter with an opening of 59 ⁇ m to obtain a sheet-like wet deposit. After air drying at room temperature, the sheet was sandwiched between polyimide films and heated at 105° C. for 5 minutes at 0.4 MPa using a heat press device to obtain a 100 ⁇ m-thick sheet C12 of Comparative Example 2 made of anion-modified pulp having acid-type carboxyl groups.
  • the unmodified softwood pulp was diluted to 0.2% by mass with ion-exchanged water and disintegrated for 10 minutes at 3000 rpm using a pulper to prepare a pulp suspension.
  • the pulp suspension was mixed with the above-mentioned suspension B12 of anion-modified pulp having an acid-type carboxy group in a mass ratio of 50:50. This was filtered under reduced pressure using a nylon mesh filter with an opening of 59 ⁇ m to obtain a sheet-like wet deposit. After air drying at room temperature, the mixture was sandwiched between polyimide films and heated at 105° C. for 5 minutes at 0.4 MPa using a heat press device to obtain a composite sheet D12 of anion-modified pulp having an acid-type carboxy group and unmodified pulp.
  • the suspension B13 was filtered under reduced pressure through a nylon mesh filter with an opening of 59 ⁇ m to obtain a sheet-like wet deposit. After air drying at room temperature, the deposit was sandwiched between polyimide films and heated at 105° C. for 5 minutes at 0.4 MPa using a heat press device to obtain a 100 ⁇ m-thick sheet C13 of Comparative Example 3 made of an anion-modified pulp having a TBA salt type carboxy group.
  • the unmodified softwood pulp was diluted to 0.2% by mass with ion-exchanged water and disintegrated for 10 minutes at 3000 rpm using a pulper to prepare a pulp suspension.
  • the pulp suspension was mixed with the suspension B13 of anion-modified pulp having a TBA salt type carboxy group obtained in the neutralization step in a mass ratio of 50:50. This was filtered under reduced pressure using a nylon mesh filter with an opening of 59 ⁇ m to obtain a sheet-like wet deposit. After air drying at room temperature, the mixture was sandwiched between polyimide films and heated at 105° C. for 5 minutes at 0.4 MPa using a heat press device to obtain a composite sheet D13 of anion-modified pulp having a TBA (tetrabutylammonium) salt type carboxy group and unmodified pulp.
  • TBA tetrabutylammonium
  • the ratio of polyvalent metal salt was measured for sheets C1 to 9 of Examples 1 to 9 and sheet C15 of Comparative Example 5 prepared as above.
  • the flame retardancy and tensile strength were evaluated for these sheets C1 to 9 and C15, and sheets C11 to 13 of Comparative Examples 1 to 3.
  • the flame retardancy was evaluated for composite sheets D1 to 9 of Examples 1 to 9 and composite sheets D11 to 15 of Comparative Examples 1 to 5. The results are shown in Table 1.
  • Comparative Example 1 As shown in Table 1, there was no flame retardancy in Comparative Example 1, which was a sheet made of unmodified pulp, as well as in Comparative Examples 2 and 3, which were anion-modified pulp with a counter ion that was not a metal ion.
  • Examples 1 to 9 where the counter ion of the anion-modified pulp was a metal ion and the amount of anionic groups was equal to or greater than the prescribed amount, not only the sheets of the anion-modified pulp alone but also the composite sheets with unmodified pulp were flame retardant. Furthermore, in Examples 1 to 9, the tensile strength was improved compared to sheets made of unmodified pulp or anion-modified pulp other than metal salts. The tensile strength tended to be higher when the anionic group was a carboxyl group than when the anionic group was a phosphate group or sulfate group. Furthermore, when it came to metal ions used as counter ions, polyvalent metals were superior to monovalent metals in flame retardancy and tensile strength.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Biochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Textile Engineering (AREA)
  • Paper (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Fireproofing Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention fournit un nouveau matériau ignifuge et une nouvelle feuille ignifuge qui contiennent une pâte modifiée par des anions. Plus précisément, le matériau ignifuge et la feuille ignifuge de l'invention contiennent une pâte modifiée par des anions dans laquelle des contre-ions d'un groupe anionique incluent des ions métalliques. La pâte modifiée par des anions présente une quantité de groupes anioniques mesurée en convertissant l'ensemble des groupes anionique en acide, comprise entre １,１ et ３,０ｍｍｏｌ／ｇ.
PCT/JP2024/041364 2023-11-30 2024-11-22 Matériau ignifuge, et feuille ignifuge Pending WO2025115763A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2023-202463 2023-11-30
JP2023202463A JP2025088036A (ja) 2023-11-30 2023-11-30 難燃性材料及び難燃性シート

Publications (1)

Publication Number Publication Date
WO2025115763A1 true WO2025115763A1 (fr) 2025-06-05

Family

ID=95896606

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2024/041364 Pending WO2025115763A1 (fr) 2023-11-30 2024-11-22 Matériau ignifuge, et feuille ignifuge

Country Status (3)

Country Link
JP (1) JP2025088036A (fr)
TW (1) TW202523708A (fr)
WO (1) WO2025115763A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020059860A1 (fr) * 2018-09-20 2020-03-26 日本製紙株式会社 Procédé de production de fibre de cellulose fine, et papier la contenant
JP2020132653A (ja) * 2019-02-12 2020-08-31 王子ホールディングス株式会社 繊維状セルロース含有樹脂組成物、液状組成物、成形体及び成形体の製造方法
JP2021095557A (ja) * 2019-08-02 2021-06-24 花王株式会社 疎水変性セルロース繊維を含有する乳化組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020059860A1 (fr) * 2018-09-20 2020-03-26 日本製紙株式会社 Procédé de production de fibre de cellulose fine, et papier la contenant
JP2020132653A (ja) * 2019-02-12 2020-08-31 王子ホールディングス株式会社 繊維状セルロース含有樹脂組成物、液状組成物、成形体及び成形体の製造方法
JP2021095557A (ja) * 2019-08-02 2021-06-24 花王株式会社 疎水変性セルロース繊維を含有する乳化組成物

Also Published As

Publication number Publication date
JP2025088036A (ja) 2025-06-11
TW202523708A (zh) 2025-06-16

Similar Documents

Publication Publication Date Title
JP6516854B2 (ja) セルロース繊維と無機粒子の複合体
JP2874973B2 (ja) 重合体変性繊維状パルプを含有する吸収性紙とその湿式抄紙法
JP6132020B2 (ja) 微細繊維含有シートの製造方法
JP6404411B2 (ja) パルプモールド
JP6927969B2 (ja) 全熱交換素子用紙
KR20160008607A (ko) 인산에스테르화 미세 셀룰로오스 섬유 및 그 제조 방법
US11186952B2 (en) Composition which contains composite fibers composed of inorganic particles and fibers
JP2016166444A (ja) 紙または板紙の抄造方法
JP2019031770A (ja) シート
JP7077111B2 (ja) パルプモールド
EP3604671B1 (fr) Procédé de fabrication d'une feuille de fibres composites à particules inorganiques
WO2025115763A1 (fr) Matériau ignifuge, et feuille ignifuge
JP7119609B2 (ja) シート及びシートの製造方法
US20210324583A1 (en) Method for analyzing structures comprising a fiber and inorganic particles
JP2020020060A (ja) シート
JP2024175362A (ja) 繊維シート及びその製造方法
JP6741106B1 (ja) シート及びシートの製造方法
JP6127697B2 (ja) 微細繊維状セルロース含有シートの製造方法
JP6711432B2 (ja) セルロースシート
JP2020172738A (ja) シート及びシートの製造方法
JP2025088041A (ja) 難燃性コーティング剤及び難燃性シート
JP7769524B2 (ja) 抗ウイルス性板紙
JP6701977B2 (ja) フィルター
JP7793907B2 (ja) 液状組成物、シート及び積層体
JP7763635B2 (ja) 微細セルロース繊維の製造方法及び微細セルロース繊維

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24897449

Country of ref document: EP

Kind code of ref document: A1