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WO2018003492A1 - Papier pour élément de ventilation à récupération d'énergie - Google Patents

Papier pour élément de ventilation à récupération d'énergie Download PDF

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Publication number
WO2018003492A1
WO2018003492A1 PCT/JP2017/021890 JP2017021890W WO2018003492A1 WO 2018003492 A1 WO2018003492 A1 WO 2018003492A1 JP 2017021890 W JP2017021890 W JP 2017021890W WO 2018003492 A1 WO2018003492 A1 WO 2018003492A1
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WIPO (PCT)
Prior art keywords
cellulose
paper
less
heat exchange
weight
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.)
Ceased
Application number
PCT/JP2017/021890
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English (en)
Japanese (ja)
Inventor
貴史 川崎
健嗣 藤井
良明 石野
正美 松浦
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.)
Nippon Paper Industries Co Ltd
Jujo Paper Co Ltd
Nippon Paper Papylia Co Ltd
Original Assignee
Nippon Paper Industries Co Ltd
Jujo Paper Co Ltd
Nippon Paper Papylia 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 Nippon Paper Industries Co Ltd, Jujo Paper Co Ltd, Nippon Paper Papylia Co Ltd filed Critical Nippon Paper Industries Co Ltd
Priority to JP2018525028A priority Critical patent/JP6927969B2/ja
Publication of WO2018003492A1 publication Critical patent/WO2018003492A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • D21H11/18—Highly hydrated, swollen or fibrillatable fibres
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
    • F24F7/00—Ventilation
    • F24F7/04—Ventilation with ducting systems, e.g. by double walls; with natural circulation
    • F24F7/06—Ventilation with ducting systems, e.g. by double walls; with natural circulation with forced air circulation, e.g. by fan positioning of a ventilator in or against a conduit
    • F24F7/08—Ventilation with ducting systems, e.g. by double walls; with natural circulation with forced air circulation, e.g. by fan positioning of a ventilator in or against a conduit with separate ducts for supplied and exhausted air with provisions for reversal of the input and output systems
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working

Definitions

  • the present invention relates to a total heat exchange element sheet used for a total heat exchanger element that performs heat exchange of both sensible heat and latent heat in a laminated structure heat exchange ventilator used in the air conditioning field.
  • This heat exchanger is composed of a plate-like partition plate having heat conductivity and moisture permeability and a spacing plate that is sandwiched between two partition plates to secure an air flow path, and the partition plates and the spacing plates are stacked in multiple layers. It has a basic structure.
  • the spacing plate is a corrugated plate formed into a sawtooth or sinusoidal waveform, and is sandwiched between partition plates by alternately changing the waveform forming direction in the orthogonal direction. Thereby, it is comprised so that the fluid path
  • the partition plate separates the air supply path that introduces fresh outdoor air into the room and the exhaust path that discharges dirty indoor air to the outdoor, and exchanges sensible heat and latent heat between the air supply and exhaust. It has a function to perform. For this reason, the water vapor permeability indicated by heat conductivity and moisture permeability is essential for the partition plate, and in addition, flame retardance and air shielding properties so that air supply and exhaust do not mix are required.
  • Total heat exchange element paper is used as a material for the partition plate that can meet such requirements, and the following prior art is disclosed.
  • Patent Document 1 discloses a total heat exchanger element paper having moisture absorption / release properties and air shielding properties obtained by impregnating or coating a porous substrate with a mixed solution of a moisture absorbent and a water-soluble polymer substance.
  • Patent Document 2 discloses a total heat exchange element paper that is superior in air shielding and hygroscopicity without using a water-soluble polymer substance by applying a hygroscopic agent to a base paper made from a raw material with a high beating degree. Is disclosed.
  • Patent Document 3 describes a partition member for a heat exchanger having a thickness of 10 to 50 microns and having an excellent air shielding property in which an alkali metal salt is blended with a hygroscopic agent.
  • Patent Document 4 discloses a moisture-absorbing / releasing total heat exchanger paper obtained by mixing microfibrillated cellulose and moisture-absorbing / releasing powder silica gel or aluminum hydroxide into papermaking fibers.
  • Patent Document 5 discloses a total heat exchanger paper using a paper base material using calcium chloride as a hygroscopic agent and blending an antiblocking agent.
  • the total heat exchange element paper a paper in which a porous substrate as described in Patent Document 1 is impregnated or coated with a mixed solution of a hygroscopic agent and a water-soluble polymer substance has been used for the partition member.
  • a part of the water-soluble polymer substance melts and blocks due to moisture absorption, and when corrugating in the element manufacturing process, There is a problem that work efficiency is lowered due to breakage or sticking of a corrugator to a press roll.
  • the base paper has a high beating degree, the water squeezing at the time of papermaking deteriorates and the production efficiency decreases, and the obtained base paper becomes brittle and easily torn, and the workability decreases when producing a heat exchange unit. There is a problem.
  • the total heat exchange element paper containing silica gel and aluminum hydroxide, which are water-insoluble moisture-absorbing and desorbing powders, and adding microfibrillated cellulose as a sealing material is moisture-absorbing and desorbing.
  • the basis weight is increased to 120 g / m 2
  • the air permeability resistance is as low as 200 seconds, and high air shielding properties cannot be obtained.
  • the raw material beaten up to 200 to 600 ml with irregular freeness (according to JIS P8121 except that the amount of collected pulp is 0.3 g) is used as the normal freeness.
  • the beating is so high that the squeezing ability during paper making deteriorates and the production efficiency decreases, and the obtained base paper becomes brittle and easy to tear, and the processability when producing the heat exchange unit May decrease.
  • the total heat exchange element paper obtained by impregnating or coating the base paper with a hygroscopic agent and a water-soluble polymer substance is easily blocked, while the high-beaten base paper is impregnated or coated with the hygroscopic agent.
  • the total heat exchange element paper imparted with moisture absorption / release properties and air shielding by processing has a problem that the production efficiency at the time of papermaking and the workability at the production of the heat exchange unit may be lowered.
  • An object of the present invention is to provide a total heat exchange element sheet having high production efficiency at the time of papermaking, hardly causing problems such as paper breakage at the time of element processing, and having high moisture absorption / release properties and air shielding properties.
  • a total heat exchange element paper comprising papermaking fibers, a hygroscopic agent, and cellulose nanofibers.
  • the papermaking fiber is a cellulose fiber.
  • the cellulose nanofiber is at least one of carboxymethylated cellulose nanofiber, carboxylated cellulose nanofiber, cationized cellulose nanofiber, and esterified cellulose nanofiber.
  • the hygroscopic agent is any one of an alkali metal salt and an alkaline earth metal salt. ⁇ 3.
  • Air permeability resistance is 700 seconds or more.
  • the total heat exchange element paper of the present invention has excellent air permeability resistance and moisture permeability by blending cellulose nanofibers, and can be suitably used for a heat exchanger. Since the total heat exchange element paper of the present invention does not require the use of a high-beating base paper, it can prevent a reduction in production efficiency and a weakening of the base paper by making the base paper high-beating. it can. Further, the total heat exchange element paper of the present invention can reduce the coating amount of the water-soluble polymer substance, and in some cases, the water-soluble polymer substance is unnecessary, so that blocking is difficult to occur, handling property, processing Excellent in properties.
  • Papermaking fiber used as a raw material for the total heat exchange element paper of the present invention is obtained from wood pulp such as softwood pulp and hardwood pulp, flax, abaca, kenaf, bamboo, bagasse and other non-wood raw materials. And cellulose fibers obtained from non-wood pulp and the like. There are no particular restrictions on the method of cooking the cellulose fibers, the presence or absence of bleaching, and the bleaching method. In addition to cellulose fibers, synthetic fibers such as polyester fibers, nylon fibers, rayon fibers, lyocell fibers, and semi-synthetic fibers can be blended for the purpose of improving adhesiveness, dimensional stability, and formability.
  • the pulp used in the present invention is beaten in a range of 100 ml CSF or more and 500 ml CSF or less with Canadian standard freeness described in JIS P8121, more preferably beaten in a range of 200 ml CSF or more and 300 ml CSF or less.
  • Canadian standard freeness is less than 100 ml CSF
  • the paper base is densified and the gaps are reduced.
  • a general beating device such as a beater or a refiner can be used, and there are no particular restrictions on the beating device or beating method.
  • the above beaten pulp contains synthetic or semi-synthetic fiber, filler, colorant, paper strength enhancer, wet strength enhancer, sulfate band, cationized starch, yield improver, etc. as necessary. To be prepared.
  • the above-mentioned stock is made by a general paper making method using a long paper machine, a circular paper machine, a short paper machine, a twin wire paper machine, or a paper machine that combines them.
  • a paper machine that combines them.
  • impregnate flame retardants, rust preventives, anti-blocking agents, etc. with an on-machine coating device such as a size press or roll coater, and apply calendering with a machine calender, super calender, soft nip calender, etc.
  • a base paper is obtained.
  • the air resistance of the base paper is improved by the sealing action of the cellulose nanofibers impregnated or coated on the base paper, but in order to fully exhibit the effect, the air resistance of the base paper itself is 50 seconds. It is necessary that the time is not less than 650 seconds, preferably not less than 150 seconds and not more than 600 seconds, more preferably not less than 200 seconds and not more than 500 seconds. When the air resistance of the base paper is less than 50 seconds, even if cellulose nanofibers are added by impregnation or coating, the air resistance after the addition is small, and the air shielding property of the total heat exchange element paper is insufficient. .
  • the air resistance of the base paper can be adjusted by a normal papermaking technique by changing the degree of beating of the pulp blended as the papermaking fiber and the basis weight of the base paper.
  • the total heat exchange element paper of the present invention can be obtained by impregnating the base paper with a chemical solution containing cellulose nanofibers and a hygroscopic agent, or coating it on at least one side.
  • Cellulose nanofibers are fine fibers obtained by subjecting a cellulose raw material to a chemical modification treatment as necessary, followed by a fibrillation treatment.
  • the average fiber diameter of the cellulose nanofiber is usually about 3 nm to 500 nm.
  • the average fiber diameter and the average fiber length can be obtained by averaging the fiber diameter and the fiber length obtained from the result of observing 30 or more fibers using a field emission scanning electron microscope (FE-SEM). .
  • the average aspect ratio of the cellulose nanofiber is usually 10 or more. Although an upper limit is not specifically limited, Usually, it is 1000 or less.
  • the origin of the cellulose raw material that is the raw material of the cellulose nanofiber is not particularly limited.
  • plants for example, wood, bamboo, hemp, jute, kenaf, farmland waste, cloth, pulp (conifers) Unbleached Kraft Pulp (NUKP), Conifer Bleached Kraft Pulp (NBKP), Hardwood Unbleached Kraft Pulp (LUKP), Hardwood Bleached Kraft Pulp (LBKP), Conifer Unbleached Sulfite Pulp (NUSP), Conifer Bleached Sulfite Pulp (NBSP) ), Thermomechanical pulp (TMP), recycled pulp, waste paper, etc.), animals (for example, ascidians), algae, microorganisms (for example, acetic acid bacteria (acetobacter)), etc.
  • NUKP Unbleached Kraft Pulp
  • NKP Conifer Bleached Kraft Pulp
  • LKP Hardwood Unbleached Kraft Pulp
  • LKP Hardwood
  • the cellulose raw materials used in the present invention are those Either one or a combination of two or more
  • it is a plant or microorganism-derived cellulose raw material (for example, cellulose fiber), and more preferably a plant-derived cellulose raw material (for example, cellulose fiber).
  • the number average fiber diameter of the cellulose raw material is not particularly limited, but in the case of softwood kraft pulp which is a general pulp, it is about 30 ⁇ m to 60 ⁇ m, and in the case of hardwood kraft pulp, it is about 10 ⁇ m to 30 ⁇ m. In the case of other pulps, those that have undergone general refining are about 50 ⁇ m. For example, when a chip or the like having a size of several centimeters is refined, it is preferably adjusted to about 50 ⁇ m by performing mechanical treatment with a disintegrator such as a refiner or beater.
  • a disintegrator such as a refiner or beater.
  • the cellulose raw material has three hydroxyl groups per glucose unit and can be subjected to various chemical modification treatments. In the present invention, these may or may not be modified. However, the chemical modification treatment sufficiently advances the fineness of the fibers, and a uniform fiber length and fiber diameter can be obtained. It is done.
  • the modification method for modifying the cellulose raw material is not particularly limited. For example, chemical modification such as oxidation (carboxylation), etherification (carboxymethylation), cationization, esterification, phosphorylation, silane coupling, fluorination, etc. Is mentioned. Of these, oxidation (carboxylation), etherification (carboxymethylation), cationization, and esterification are preferred. These detailed methods will be described below.
  • the amount of carboxyl groups relative to the absolute dry weight of the obtained oxidized cellulose or cellulose nanofibers is preferably 0.5 mmol / g. As mentioned above, More preferably, it is 0.8 mmol / g or more, More preferably, it is 1.0 mmol / g or more.
  • the upper limit is preferably 3.0 mmol / g or less, more preferably 2.5 mmol / g or less, and still more preferably 2.0 mmol / g or less.
  • the oxidation method is not particularly limited, one example is N-oxyl compound and cellulose in water using an oxidizing agent in the presence of a substance selected from the group consisting of bromide, iodide or a mixture thereof. The method of oxidizing a raw material is mentioned.
  • the primary hydroxyl group at the C6 position of the glucopyranose ring on the cellulose surface is selectively oxidized to produce a group selected from the group consisting of an aldehyde group, a carboxyl group, and a carboxylate group.
  • concentration of the cellulose raw material at the time of reaction is not specifically limited, 5 weight% or less is preferable.
  • N-oxyl compound refers to a compound capable of generating a nitroxy radical.
  • nitroxy radicals include 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO).
  • TEMPO 2,2,6,6-tetramethylpiperidine 1-oxyl
  • any compound can be used as long as it promotes the target oxidation reaction.
  • the amount of the N-oxyl compound used is not particularly limited as long as it is a catalyst amount that can oxidize cellulose as a raw material. For example, 0.01 mmol or more is preferable and 0.02 mmol or more is more preferable with respect to 1 g of absolutely dry cellulose.
  • the upper limit is preferably 10 mmol or less, more preferably 1 mmol or less, and even more preferably 0.5 mmol or less.
  • the amount of N-oxyl compound used is preferably 0.01 mmol or more and 10 mmol or less, more preferably 0.01 mmol or more and 1 mmol or less, and further preferably 0.02 mmol or more and 0.5 mmol or less with respect to 1 g of absolutely dry cellulose.
  • Bromide is a compound containing bromine, and examples thereof include alkali metal bromide that can be dissociated and ionized in water, such as sodium bromide.
  • the iodide is a compound containing iodine, and examples thereof include alkali metal iodide. What is necessary is just to select the usage-amount of a bromide or iodide in the range which can accelerate
  • the total amount of bromide and iodide is preferably 0.1 mmol or more, more preferably 0.5 mmol or more, with respect to 1 g of absolutely dry cellulose.
  • the upper limit is preferably 100 mmol or less, more preferably 10 mmol or less, and even more preferably 5 mmol or less. Therefore, the total amount of bromide and iodide is preferably 0.1 mmol or more and 100 mmol or less, more preferably 0.1 mmol or more and 10 mmol or less, and further preferably 0.5 mmol or more and 5 mmol or less with respect to 1 g of absolutely dry cellulose.
  • the oxidizing agent is not particularly limited, and examples thereof include halogen, hypohalous acid, halous acid, perhalogen acid, salts thereof, halogen oxide, and peroxide.
  • hypohalous acid or a salt thereof is preferable because it is inexpensive and has a low environmental burden
  • hypochlorous acid or a salt thereof is more preferable
  • sodium hypochlorite is more preferable.
  • the amount of the oxidizing agent used is preferably 0.5 mmol or more, more preferably 1 mmol or more, and further preferably 3 mmol or more with respect to 1 g of absolutely dry cellulose.
  • the upper limit is preferably 500 mmol or less, more preferably 50 mmol or less, further preferably 25 mmol or less, and most preferably 10 mmol or less. Therefore, the amount of the oxidizing agent used is preferably 0.5 mmol or more and 500 mmol or less, more preferably 0.5 mmol or more and 50 mmol or less, further preferably 1 mmol or more and 25 mmol or less, and most preferably 3 mmol or more and 10 mmol or less with respect to 1 g of absolutely dry cellulose. preferable.
  • the amount of the oxidizing agent used is preferably 1 mol or more with respect to 1 mol of the N-oxyl compound.
  • the upper limit is preferably 40 mol or less. Therefore, the amount of the oxidizing agent used is preferably 1 mol or more and 40 mol or less with respect to 1 mol of the N-oxyl compound.
  • the conditions such as pH and temperature during the oxidation reaction are not particularly limited, and generally the oxidation reaction proceeds efficiently even under relatively mild conditions.
  • the reaction temperature is preferably 4 ° C or higher, more preferably 15 ° C or higher.
  • the upper limit is preferably 40 ° C. or lower, and more preferably 30 ° C. or lower. Therefore, the temperature is preferably 4 ° C. or higher and 40 ° C. or lower, and may be 15 ° C. or higher and 30 ° C. or lower, that is, room temperature.
  • the pH of the reaction solution is preferably 8 or more, and more preferably 10 or more.
  • the upper limit is preferably 12 or less, and more preferably 11 or less.
  • the pH of the reaction solution is preferably 8 or more and 12 or less, more preferably 10 or more and 11 or less.
  • a carboxyl group is generated in cellulose as the oxidation reaction proceeds, and therefore the pH of the reaction solution tends to decrease. Therefore, in order to advance the oxidation reaction efficiently, it is preferable to add an alkaline solution such as an aqueous sodium hydroxide solution to maintain the pH of the reaction solution in the above range.
  • the reaction medium for the oxidation is preferably water for reasons such as ease of handling and the difficulty of side reactions.
  • the reaction time in the oxidation can be appropriately set according to the progress of the oxidation, and is usually 0.5 hours or longer.
  • the upper limit is usually 6 hours or less, preferably 4 hours or less. Therefore, the reaction time in oxidation is usually 0.5 hours or more and 6 hours or less, for example 0.5 hours or more and 4 hours or less.
  • Oxidation may be carried out in two or more stages. For example, the oxidized cellulose obtained by filtration after the completion of the first stage reaction is oxidized again under the same or different reaction conditions, thereby preventing the reaction from being inhibited by the salt produced as a by-product in the first stage reaction. Can be oxidized well.
  • Another example of the carboxylation (oxidation) method is a method of oxidizing by ozone treatment.
  • the ozone treatment is usually performed by bringing a gas containing ozone and a cellulose raw material into contact with each other.
  • the ozone concentration in the gas is preferably 50 g / m 3 or more.
  • the upper limit is preferably 250 g / m 3 or less, and more preferably 220 g / m 3 or less.
  • the ozone concentration in the gas is preferably at most 50 g / m 3 or more 250 g / m 3, more preferably at most 50 g / m 3 or more 220 g / m 3.
  • the amount of ozone added is preferably 0.1% by weight or more, and more preferably 5% by weight or more, based on 100% by weight of the solid content of the cellulose raw material.
  • the upper limit is usually 30% by weight or less. Therefore, the amount of ozone added is preferably 0.1% by weight to 30% by weight and more preferably 5% by weight to 30% by weight with respect to 100% by weight of the solid content of the cellulose raw material.
  • the ozone treatment temperature is usually 0 ° C. or higher, preferably 20 ° C. or higher.
  • the upper limit is usually 50 ° C. or lower. Therefore, the ozone treatment temperature is usually 0 ° C. or higher and 50 ° C. or lower, and preferably 20 ° C. or higher and 50 ° C. or lower.
  • the ozone treatment time is usually 1 minute or longer, preferably 30 minutes or longer.
  • the upper limit is usually 360 minutes or less. Therefore, the ozone treatment time is usually from 1 minute to 360 minutes, preferably from 30 minutes to 360 minutes.
  • the resulting product obtained after the ozone treatment may be further oxidized using an oxidizing agent.
  • the oxidizing agent used for the additional oxidation treatment is not particularly limited, and examples thereof include chlorine compounds such as chlorine dioxide and sodium chlorite; oxygen, hydrogen peroxide, persulfuric acid, peracetic acid and the like.
  • Examples of the method for the additional oxidation treatment include a method in which these oxidizing agents are dissolved in a polar organic solvent such as water or alcohol to prepare an oxidizing agent solution, and the cellulose raw material is immersed in the oxidizing agent solution.
  • the amount of the carboxyl group, carboxylate group, and aldehyde group contained in the oxidized cellulose nanofiber can be adjusted by controlling the oxidizing conditions such as the addition amount of the oxidizing agent and the reaction time.
  • An example of a method for measuring the amount of carboxyl groups will be described below. Prepare 60 ml of 0.5 wt% slurry (aqueous dispersion) of oxidized cellulose and add 0.1 M hydrochloric acid aqueous solution to pH 2.5, then add 0.05 N sodium hydroxide aqueous solution dropwise to adjust pH to 11.
  • (2-2-2) Etherified (Carboxymethylated) Cellulose Nanofiber Etherification includes carboxymethyl (ether), methyl (ether), ethyl (ether), cyanoethyl (ether), hydroxyethyl ( Examples include ether), hydroxypropyl (ether), ethylhydroxyethyl (ether), and hydroxypropylmethyl (ether).
  • a carboxymethylation method will be described below.
  • the degree of carboxymethyl group substitution per anhydroglucose unit in the obtained carboxymethylated cellulose or cellulose nanofiber is preferably 0.01 or more, more preferably 0.05 or more, More preferably, it is 0.10 or more.
  • the upper limit is preferably 0.50 or less, more preferably 0.40 or less, and even more preferably 0.35 or less. Therefore, the degree of carboxymethyl group substitution is preferably from 0.01 to 0.50, more preferably from 0.05 to 0.40, and even more preferably from 0.10 to 0.35.
  • the method of carboxymethylation is not particularly limited, and examples thereof include a method of mercerizing a cellulose raw material as a bottoming raw material and then etherifying.
  • the solvent used for the carboxymethylation reaction include water, alcohols (for example, lower alcohols), and mixed solvents thereof.
  • the lower alcohol include methanol, ethanol, N-propyl alcohol, isopropyl alcohol, N-butanol, isobutanol, and tertiary butanol.
  • the mixing ratio of the lower alcohol in the mixed solvent is usually 60% by weight or more and 95% by weight or less.
  • the amount of the solvent is usually 3 times the weight of the cellulose raw material. Although an upper limit is not specifically limited, It is 20 weight times. Therefore, the amount of the solvent is preferably 3 to 20 times by weight.
  • Mercerization is usually performed by mixing a bottoming raw material and a mercerizing agent.
  • mercerizing agents include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
  • the amount of mercerizing agent used is preferably 0.5 times mol or more, more preferably 1.0 times mol or more, and further preferably 1.5 times mol or more per anhydroglucose residue of the starting material.
  • the upper limit is usually 20 times mole or less, preferably 10 times mole or less, and more preferably 5 times mole or less.
  • the mercerization reaction temperature is usually 0 ° C. or higher, preferably 10 ° C. or higher.
  • the upper limit is usually 70 ° C. or lower, preferably 60 ° C. or lower. Therefore, the reaction temperature is usually 0 ° C. or higher and 70 ° C. or lower, preferably 10 ° C. or higher and 60 ° C. or lower.
  • the reaction time is usually 15 minutes or longer, preferably 30 minutes or longer.
  • the upper limit is usually 8 hours or less, preferably 7 hours or less. Therefore, it is usually from 15 minutes to 8 hours, preferably from 30 minutes to 7 hours.
  • the etherification reaction is usually performed by adding a carboxymethylating agent to the reaction system after mercerization.
  • the carboxymethylating agent include sodium monochloroacetate.
  • the addition amount of the carboxymethylating agent is usually preferably 0.05 times mol or more, more preferably 0.5 times mol or more, and further preferably 0.8 times mol or more per glucose residue of the cellulose raw material.
  • the upper limit is usually 10.0 times mol or less, preferably 5 times mol or less, more preferably 3 times mol or less, and thus preferably 0.05 times mol or more and 10.0 times mol or less, more preferably It is 0.5 times mole or more and 5 times mole or less, More preferably, it is 0.8 times mole or more and 3 times mole or less.
  • the reaction temperature is usually 30 ° C. or higher, preferably 40 ° C. or higher, and the upper limit is usually 90 ° C. or lower, preferably 80 ° C. or lower. Accordingly, the reaction temperature is usually 30 ° C. or higher and 90 ° C. or lower, preferably 40 ° C. or higher and 80 ° C. or lower.
  • the reaction time is usually 30 minutes or longer, preferably 1 hour or longer.
  • the upper limit is usually 10 hours or less, preferably 4 hours or less. Therefore, the reaction time is usually from 30 minutes to 10 hours, preferably from 1 hour to 4 hours.
  • the reaction solution may be stirred as necessary during the carboxymethylation reaction.
  • the measurement of the degree of carboxymethyl substitution per glucose unit of carboxymethylated cellulose nanofibers may be performed, for example, by the following method. That is, 1) About 2.0 g of carboxymethylated cellulose (absolutely dry) is precisely weighed and put into a 300 mL conical stoppered Erlenmeyer flask. 2) Add 100 mL of a solution obtained by adding 100 mL of special grade concentrated nitric acid to 1000 mL of nitric acid methanol and shake for 3 hours to convert the carboxymethylcellulose salt (carboxymethylated cellulose) to hydrogen-type carboxymethylated cellulose.
  • (2-2-3) Cationized cellulose nanofiber When the cellulose raw material is modified by cationization, the resulting cationized cellulose nanofiber has a cation such as ammonium, phosphonium, sulfonium, or a group having the cation in the molecule. It only has to be included.
  • the cationized cellulose nanofiber preferably includes a group having ammonium, and more preferably includes a group having quaternary ammonium.
  • the cationization method is not particularly limited, and examples thereof include a method of reacting a cellulose raw material with a cationizing agent and a catalyst in the presence of water and / or alcohol.
  • the cationizing agent include glycidyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltrialkylammonium hydride (eg, 3-chloro-2-hydroxypropyltrimethylammonium hydride) or a halohydrin type thereof. By using any of these, a cationized cellulose having a group containing quaternary ammonium can be obtained.
  • the catalyst include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
  • the alcohol examples include alcohols having 1 to 4 carbon atoms.
  • the amount of the cationizing agent is preferably 5% by weight or more, more preferably 10% by weight or more with respect to 100% by weight of the cellulose raw material.
  • the upper limit is usually 800% by weight or less, preferably 500% by weight or less.
  • the amount of the catalyst is preferably 0.5% by weight or more, more preferably 1% by weight or more with respect to 100% by weight of the cellulose fibers.
  • the upper limit is usually 7% by weight or less, preferably 3% by weight or less.
  • the amount of alcohol is preferably 50% by weight or more, more preferably 100% by weight or more, based on 100% by weight of cellulose fibers.
  • the upper limit is usually 50000% by weight or less, preferably 500% by weight or less.
  • the reaction temperature at the time of cationization is usually 10 ° C or higher, preferably 30 ° C or higher, and the upper limit is usually 90 ° C or lower, preferably 80 ° C or lower.
  • the reaction time is usually 10 minutes or longer, preferably 30 minutes or longer.
  • the upper limit is usually 10 hours or less, preferably 5 hours or less.
  • the reaction solution may be stirred as necessary during the cationization reaction.
  • the degree of cation substitution per glucose unit in the cationized cellulose can be adjusted by controlling the amount of cationizing agent added and the composition ratio of water and / or alcohol.
  • the degree of cation substitution refers to the number of substituents introduced per unit structure (glucopyranose ring) constituting cellulose.
  • the degree of cation substitution is defined as “a value obtained by dividing the number of moles of the introduced substituent by the total number of moles of hydroxyl groups of the glucopyranose ring”. Since pure cellulose has three substitutable hydroxyl groups per unit structure (glucopyranose ring), the theoretical maximum value of the degree of cation substitution is 3 (the minimum value is 0).
  • the cation substitution degree per glucose unit of the cationized cellulose nanofiber is preferably 0.01 or more, more preferably 0.02 or more, and further preferably 0.03 or more.
  • the upper limit is preferably 0.40 or less, more preferably 0.30 or less, and further preferably 0.20 or less. Therefore, it is preferably 0.01 or more and 0.40 or less, more preferably 0.02 or more and 0.30 or less, and further preferably 0.03 or more and 0.20 or less.
  • the method of esterification is not particularly limited, and examples thereof include a method of reacting the following compound A with a cellulose raw material.
  • Examples of the method of reacting compound A with a cellulose raw material include a method of mixing a powder or an aqueous solution of compound A with a cellulose raw material, a method of adding an aqueous solution of compound A to a slurry of a cellulose raw material, and the like.
  • a method of mixing an aqueous solution of Compound A into a cellulose raw material or a slurry thereof is preferable.
  • compound A examples include phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, polyphosphonic acid, and esters thereof.
  • Compound A may be in the form of a salt.
  • a phosphoric acid compound is preferable because it is low in cost and easy to handle, and a phosphoric acid group can be introduced into cellulose of pulp fiber to improve the fibrillation efficiency.
  • the phosphate compound may be any compound having a phosphate group.
  • phosphoric acid sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate, sodium metaphosphate, diphosphate
  • examples include potassium hydrogen, dipotassium hydrogen phosphate, tripotassium phosphate, potassium pyrophosphate, potassium metaphosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, and ammonium metaphosphate.
  • the phosphoric acid compound used may be one type or a combination of two or more types.
  • phosphoric acid, phosphoric acid sodium salt, phosphoric acid potassium salt, phosphoric acid from the viewpoint that phosphoric acid group introduction efficiency is high, is easy to be defibrated in the following defibrating process, and is industrially applicable.
  • sodium dihydrogen phosphate and disodium hydrogen phosphate are more preferred.
  • the pH of the aqueous solution of the phosphoric acid compound is preferably 7 or less from the viewpoint of increasing the efficiency of introducing phosphate groups, and more preferably pH 3 or more from the viewpoint of suppressing hydrolysis of the pulp fiber.
  • esterification method examples include the following methods.
  • Compound A is added to a suspension of cellulose raw material (for example, solid content concentration of 0.1 to 10% by weight) with stirring to introduce phosphate groups into the cellulose.
  • the amount of compound A added is preferably 0.2 parts by weight or more, more preferably 1 part by weight or more, as the amount of phosphorus element.
  • the upper limit is preferably 500 parts by weight or less, and more preferably 400 parts by weight or less.
  • the yield corresponding to the usage-amount of the compound A can be obtained efficiently. Therefore, it is preferably 0.2 parts by weight or more and 500 parts by weight or less, and more preferably 1 part by weight or more and 400 parts by weight or less.
  • the following compound B may be further added to the reaction system.
  • the method of adding Compound B to the reaction system include a method of adding to a slurry of cellulose raw material, an aqueous solution of Compound A, or a slurry of cellulose raw material and Compound A.
  • Compound B is a nitrogen-containing compound that exhibits basicity. “Show basic” usually means that the aqueous solution of Compound B is pink to red in the presence of a phenolphthalein indicator, or the pH of the aqueous solution of Compound B is greater than 7.
  • the nitrogen-containing compound showing basicity is not particularly limited as long as the effects of the present invention are exhibited, but a compound having an amino group is preferable.
  • urea methylamine, ethylamine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, pyridine, ethylenediamine, hexamethylenediamine and the like can be mentioned. Of these, urea is preferable because it is easy to handle at low cost.
  • the amount of Compound B added is preferably 2 parts by weight or more and 1000 parts by weight or less, and more preferably 100 parts by weight or more and 700 parts by weight or less when the cellulose raw material is 100 parts by weight.
  • the reaction temperature is preferably 0 ° C. or higher and 95 ° C. or lower, and more preferably 30 ° C. or higher and 90 ° C. or lower.
  • reaction time is not specifically limited, Usually, it is about 1 minute or more and 600 minutes or less, and 30 minutes or more and 480 minutes or less are preferable. If the conditions for the esterification reaction are in any of these ranges, it is possible to prevent cellulose from being excessively esterified and easily dissolved, and to improve the yield of phosphorylated esterified cellulose. .
  • an esterified cellulose suspension is usually obtained.
  • the esterified cellulose suspension is dehydrated as necessary, and is preferably subjected to heat treatment after dehydration. Thereby, hydrolysis of a cellulose raw material can be suppressed.
  • the heating temperature is preferably 100 ° C. or more and 170 ° C. or less, and is heated at 130 ° C. or less (more preferably 110 ° C. or less) while water is contained in the heat treatment, and after removing water, 100 ° C. or more and 170 ° C. It is more preferable to perform the heat treatment at a temperature not higher than ° C.
  • phosphate esterified cellulose In phosphate esterified cellulose, a phosphate group substituent is introduced into the cellulose raw material, and the cellulose repels electrically. Therefore, phosphorylated esterified cellulose can be easily nano-defibrated.
  • the degree of phosphate group substitution per glucose unit in the phosphate esterified cellulose is preferably 0.001 or more. Thereby, sufficient defibration (for example, nano defibration) can be implemented.
  • the upper limit is preferably 0.40. Thereby, swelling or melt
  • the phosphorylated cellulose is preferably subjected to a washing treatment such as washing with cold water after boiling. Thereby, defibration can be performed efficiently.
  • the cellulose raw material may be defibrated before or after the cellulose raw material is modified. Moreover, defibration may be performed at once or a plurality of times. In the case of multiple times, each defibration period may be any time.
  • the apparatus used for defibration is not particularly limited, and examples thereof include high-speed rotating type, colloid mill type, high-pressure type, roll mill type, ultrasonic type and the like, and high-pressure or ultra-high-pressure homogenizers are preferable, and wet high pressure Or an ultra high pressure homogenizer is more preferable.
  • the apparatus is preferably capable of applying a strong shearing force to the cellulose raw material or modified cellulose (usually a dispersion).
  • the pressure that can be applied by the apparatus is preferably 50 MPa or more, more preferably 100 MPa or more, and still more preferably 140 MPa or more.
  • the apparatus is preferably a wet high-pressure or ultrahigh-pressure homogenizer capable of applying the above pressure to a cellulose raw material or modified cellulose (usually a dispersion) and applying a strong shearing force. Thereby, defibration can be performed efficiently.
  • the solid content concentration of the cellulose raw material in the dispersion is usually 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.3%. % By weight or more.
  • the upper limit is usually 10% by weight or less, preferably 6% by weight or less.
  • liquidity can be hold
  • pretreatment may be performed as necessary. The pretreatment may be performed using a mixing, stirring, emulsifying, and dispersing device such as a high-speed shear mixer.
  • cellulose nanofibers may be used in the form of a dispersion, but if necessary, a drying process is carried out to partially or completely remove the solvent, thereby obtaining a wet solid. You may use as a thing or a dry solid.
  • the wet solid is a solid in an intermediate state between the dispersion and the dry solid.
  • the drying treatment may be performed after mixing the water-soluble polymer in the cellulose nanofiber dispersion in advance.
  • water-soluble polymers include cellulose derivatives (carboxymethyl cellulose and salts thereof, methyl cellulose, hydroxypropyl cellulose, ethyl cellulose), xanthan gum, xyloglucan, dextrin, dextran, carrageenan, locust bean gum, alginic acid, alginate, pullulan, starch, Snack flour, scrap flour, positive starch, phosphorylated starch, corn starch, gum arabic, locust bean gum, gellan gum, gellan gum, polydextrose, pectin, chitin, water-soluble chitin, chitosan, casein, albumin, soy protein lysate, peptone, polyvinyl Alcohol, polyacrylamide, sodium polyacrylate, polyvinylpyrrolidone, polyvinyl acetate, polyamino acid, polylactic acid, polymalic acid, polyg Serine, latex, rosin sizing agent, petroleum resin sizing agent, cellulose
  • the dry solid and wet solid of cellulose nanofibers may be prepared by drying a dispersion of cellulose nanofibers or a mixture of cellulose nanofibers and a water-soluble polymer.
  • a drying method is not specifically limited, For example, spray drying, pressing, air drying, hot air drying, and vacuum drying are mentioned.
  • the drying device include a continuous tunnel drying device, a band drying device, a vertical drying device, a vertical turbo drying device, a multi-stage disk drying device, an aeration drying device, a rotary drying device, an air flow drying device, and a spray dryer drying device.
  • Spray dryers cylindrical dryers, drum dryers, screw conveyor dryers, rotary dryers with heating tubes, vibration transport dryers, batch-type box dryers, vacuum box dryers, stirring dryers, etc.
  • the drying device is preferably a drum drying device.
  • the air shielding property can be enhanced by impregnating or coating the base paper.
  • Preferred coating weight of the cellulose nanofiber is a 0.2 g / m 2 or more 5.0 g / m 2 or less as a solid coating amount per one surface, preferably 0.5 g / m 2 or more 3.0 g / m 2 or less.
  • the coating amount of the cellulose nanofiber is less than 0.2 g / m 2 , the improvement of the air resistance is small and the air shielding property is insufficient.
  • the coating amount exceeds 5.0 g / m 2 , the moisture permeability decreases, which is not preferable.
  • Hygroscopic agent Hygroscopic agents include alkali metal salts such as lithium chloride and sodium lactate, alkaline earth metal salts such as calcium chloride and magnesium chloride, ammonium salts such as ammonium phosphate and ammonium sulfamate, guanidine sulfamate, A guanidine salt such as guanidine hydrochloride can be used, and particularly, calcium chloride which is excellent in hygroscopicity and inexpensive can be preferably used. These compounds may be used alone or in combination of two or more. Moreover, what can be used as a flame retardant among hygroscopic agents can also be mix
  • a preferable coating amount of the hygroscopic agent is 0.5 g / m 2 or more and 20 g / m 2 or less, preferably 1.0 g / m 2 or more and 15 g / m 2 or less.
  • the coating amount of the moisture absorbent is insufficient moisture permeability is less than 0.5 g / m 2.
  • the coating amount exceeds 20 g / m 2 , the moisture absorption amount is excessive, and there is a risk that condensation or a hygroscopic agent may flow out in a high temperature and high humidity environment.
  • the hygroscopic agent may be impregnated on the entire base paper, or may be applied on one side or both sides, as long as it is within the above coating amount range.
  • the total heat exchange element paper of the present invention is obtained by impregnating or coating a base paper composed of papermaking fibers with a chemical solution containing cellulose nanofibers and a chemical solution containing a hygroscopic agent. Can be manufactured.
  • the chemical solution containing cellulose nanofibers and the chemical solution containing a hygroscopic agent are preferably the same chemical solution because the coating amount of each component can be accurately estimated.
  • a chemical solution containing cellulose nanofibers and a hygroscopic agent can be obtained by adding a hygroscopic agent to a dispersion of cellulose nanofibers.
  • the ratio of the hygroscopic agent added to the cellulose nanofiber dispersion is 2 parts by mass or more and 30 parts by mass or less, preferably 5 parts by mass or more and 20 parts by mass or less of the hygroscopic agent with respect to 1 part by mass of the cellulose nanofibers in terms of solid content. Blend. If the amount of the hygroscopic agent is less than 2 parts by mass, sufficient moisture permeability cannot be obtained. Moreover, if the mixing ratio of the hygroscopic agent exceeds 30 parts by mass, the air resistance is insufficient, which is not preferable.
  • the chemical solution of the present invention may contain various commonly used functional auxiliaries such as water-resistant agents, flame retardants, rust inhibitors, antibacterial agents, antibacterial agents, and antiblocking agents. .
  • functional auxiliaries such as water-resistant agents, flame retardants, rust inhibitors, antibacterial agents, antibacterial agents, and antiblocking agents.
  • medical solution may be used for both surfaces, and the chemical
  • the total heat exchange element paper of the present invention can exhibit excellent air resistance by applying cellulose nanofibers.
  • the water-soluble polymer substance can be added as long as blocking does not occur, but the amount is preferably less than 2.0 g / m 2 and more preferably less than 0.5 g / m 2. preferable.
  • the water-soluble polymer substance include polyvinyl alcohol, starch, starch derivatives, polyethylene oxide, alginate, carboxymethylcellulose salt, methylcellulose, and hydroxyethylcellulose.
  • a rod coater As a method for coating a base paper with a chemical solution containing cellulose nanofibers prepared as described above, a rod coater, a die coater, a curtain coater, a 2 roll size press, a rod metalling size press, a gate roll coater, a blade
  • coating with coating machines, such as a coater, and the method of impregnation can be mentioned.
  • the method for drying the wet coating layer is not particularly limited, and various methods such as a steam heating cylinder, a hot air air dryer, a gas heater dryer, an electric heater dryer, and an infrared heater dryer can be used alone or in combination. .
  • the obtained coated paper may be calendered with a super calender, a hot-press roll or the like, if necessary.
  • a super calender a hot-press roll or the like.
  • the calendar treatment By applying the calendar treatment, the thickness is reduced and the thermal conductivity in the thickness direction is improved.
  • the air resistance is increased and the air shielding property is improved.
  • a paper containing papermaking fibers, a hygroscopic agent, and cellulose nanofibers can be obtained.
  • the paper has both air shielding properties and moisture permeability and can be suitably used as a total heat exchange element paper.
  • the basis weight of the total heat exchange element paper is preferably 10 g / m 2 or more and 70 g / m 2 or less, more preferably 15 g / m 2 or more and 40 g / m 2 or less, and most preferably 20 g / m 2 or more and 35 g / m 2. It is as follows. When the basis weight is less than 10 g / m 2 , the strength is remarkably lowered, and workability when processing into a total heat exchange element is lowered. Basis weight unfavorably lowered total heat exchange efficiency in the thickness direction exceeds 70 g / m 2.
  • the thickness of the total heat exchange element paper is preferably 8 ⁇ m or more and 80 ⁇ m or less, and a thinner one in this range is more preferable because the total heat exchange efficiency tends to increase.
  • the thickness is less than 8 ⁇ m, the strength is remarkably lowered, and workability when processing into a total heat exchange element is lowered.
  • the thickness exceeds 80 ⁇ m, the total heat exchange efficiency in the thickness direction is lowered, which is not preferable.
  • the air resistance of the total heat exchange element paper is preferably 700 seconds or more. If the air resistance is less than 700 seconds, there is no significant difference from the air resistance of the base paper, and there is no point in applying cellulose nanofibers. If the air resistance of the heat exchange element paper used in the heat exchange ventilator increases, it becomes difficult to mix air between fresh air supply and dirty exhaust air, and especially the carbon dioxide gas transfer rate decreases. The air shielding property that separates air and exhaust is improved.
  • Patent Document 3 states that when the air permeability resistance is 200 seconds or more, the carbon dioxide gas migration rate is 5% or less, and when the air permeability resistance is 5000 seconds or more, the carbon dioxide gas migration rate can be suppressed to 1% or less. According to Patent Document 5, if the air permeability resistance is 500 seconds or more, it can be used as a total heat exchange element sheet.
  • the moisture permeability of the total heat exchange element paper is preferably 800 g / m 2 ⁇ 24 hr or more, more preferably 1000 g / m 2 ⁇ 24 hr or more.
  • the moisture permeability is effective as an index of the latent heat exchange efficiency of the total heat exchange element paper. The higher the moisture permeability, the higher the latent heat exchange efficiency. On the other hand, the latent heat required when the moisture permeability is less than 800 g / m 2 ⁇ 24 hr. Exchange efficiency cannot be obtained.
  • Basis weight A sample having a size of 250 mm ⁇ 200 mm is placed in a weighing bottle with a known weight, and the weight after drying at 105 ° C. for 2 hours is measured, and the absolute dry weight per square meter of the sample is calculated. The amount was (g / m 2 ).
  • Moisture permeability Measurement was performed by changing the temperature and humidity conditions of the measurement environment using an instrument specified in JIS Z0208 (1976) moisture permeability (cup method).
  • the moisture permeable cup equipped with the test piece is left in a constant temperature and humidity chamber set at 20 ° C. and 65% RH for 24 hours to measure the weight increase, and the weight change per 24 hours of the measurement area of 1 square meter is calculated.
  • the water vapor transmission rate (g / m 2 ⁇ 24 hr) was obtained.
  • Air permeability resistance The average value of five measurements was calculated based on the Oken type testing machine method described in JIS P8117 (2009) Air permeability and air resistance, and the air resistance (king Ken) (seconds).
  • CM-CNF carboxymethylated cellulose nanofibers
  • Example 1 45 parts by mass of water and 17.6 parts by mass of calcium chloride (manufactured by Central Glass Co., Ltd.) are added to 90 parts by mass of an aqueous CM-CNF dispersion (solid content: 1.2% by mass), and dispersed with a bladed stirrer. Then, it was dissolved to prepare a coating solution. The above coating solution was applied to one side of the base paper with a Meyer bar and dried to obtain the total heat exchange element paper of the present invention. The adhesion amount, the air resistance, and the moisture permeability of this paper were measured. The results are shown in Table 1.
  • Example 2 Coating is performed by adding 5.52 parts by mass of calcium chloride (manufactured by Central Glass Co., Ltd.) to 90 parts by mass of an aqueous CM-CNF dispersion (solid content: 1.2% by mass) and dispersing and dissolving with a bladed stirrer. A liquid was prepared. The coating solution was applied to one side of the base paper with a Meyer bar and dried to obtain the total heat exchange element paper of the present invention. The adhesion amount, the air resistance, and the moisture permeability of this paper were measured. The results are shown in Table 1.
  • Example 3 A total heat exchange element sheet of the present invention was obtained in the same manner as in Example 2 except that the calcium chloride content was 11.7 parts by mass. The adhesion amount, the air resistance, and the moisture permeability of this paper were measured. The results are shown in Table 1.
  • Example 4 30 parts by mass of water and 11.7 parts by mass of calcium chloride (manufactured by Central Glass Co., Ltd.) are added to 60 parts by mass of an aqueous CM-CNF dispersion (solid content: 1.2% by mass) and dispersed with a bladed stirrer. Then, it was dissolved to prepare a coating solution. The coating solution was applied to one side of the base paper with a Meyer bar and dried to obtain the total heat exchange element paper of the present invention. The adhesion amount, air resistance, and moisture permeability of this paper were measured and shown in Table 1.
  • T-CNF carboxylated cellulose nanofiber
  • Example 5 60 parts by mass of water and 25.2 parts by mass of calcium chloride (manufactured by Central Glass Co., Ltd.) are added to 120 parts by mass of an aqueous dispersion of T-CNF (solid concentration: 1.1% by mass), and dispersed with a bladed stirrer. Then, it was dissolved to prepare a coating solution. The coating liquid was applied to one side of the base paper with a Meyer bar and dried to obtain a single-side coated paper of T-CNF and calcium chloride.
  • this single-sided coated paper On the other side of this single-sided coated paper, 45 parts by mass of water was added to 90 parts by mass of an aqueous T-CNF dispersion (solid content concentration: 1.1% by mass), and the coating liquid dispersed with a bladed stirrer was applied to Meyer. After coating with a bar, the sheet was dried to obtain the total heat exchange element paper of the present invention coated on both sides. The adhesion amount, the air resistance, and the moisture permeability of this paper were measured. The results are shown in Table 1.
  • C-CNF cationized cellulose nanofibers
  • Example 6 45 parts by weight of water and 17.6 parts by weight of calcium chloride (manufactured by Central Glass Co., Ltd.) are added to 90 parts by weight of an aqueous dispersion of C-CNF (solid content concentration: 1.2% by weight) and dispersed with a bladed stirrer. Then, it was dissolved to prepare a coating solution. The coating solution was applied to one side of the base paper with a Meyer bar and dried to obtain a single-side coated paper of C-CNF and calcium chloride.
  • Example 7 45 parts by mass of water and 17.6 parts by mass of calcium chloride (manufactured by Central Glass Co., Ltd.) are added to 90 parts by mass of an aqueous CM-CNF dispersion (solid content: 1.2% by mass), and dispersed with a bladed stirrer. Then, it was dissolved to prepare a coating solution. The coating solution was applied to one side of the base paper with a Meyer bar and dried to obtain a single-side coated paper of CM-CNF and calcium chloride.
  • Example 8 30 parts by weight of water and 3.6 parts by weight of potassium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) were added to 60 parts by weight of an aqueous CM-CNF dispersion (solid content 1.2% by weight), and a bladed stirrer The coating solution was prepared by dispersing and dissolving the solution. The coating solution was applied to one side of the base paper with a Meyer bar and dried to obtain the total heat exchange element paper of the present invention. The adhesion amount, the air resistance, and the moisture permeability of this paper were measured. The results are shown in Table 1.
  • Example 9 30 parts by mass of water and 3.6 parts by mass of lithium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) were added to 60 parts by mass of an aqueous dispersion of CM-CNF (solid content concentration 1.2% by mass), and a bladed stirrer The coating solution was prepared by dispersing and dissolving the solution. The coating solution was applied to one side of the base paper with a Meyer bar and dried to obtain the total heat exchange element paper of the present invention. The adhesion amount, the air resistance, and the moisture permeability of this paper were measured. The results are shown in Table 1.
  • One end in the longitudinal direction of the bonded test piece is peeled off slightly, and one end is sandwiched between sample grips attached to a digital force gauge (manufactured by Nidec Shinpo Co., Ltd., device name: FGP-0.5 type), The other end of the sheet was grasped by hand and pulled, peeled about 70 mm in the longitudinal direction, and the maximum value of the peel resistance was read to obtain the peel resistance per 5 cm of the sample width.
  • the peel resistance of the test piece force-bonded using a hot-press roll was 50 g / 5 cm or less, and the blocking property was evaluated to be extremely weak. Moreover, also in the blocking properties of the other examples, a part of the pressure-bonding did not peel off, and the base material was not destroyed.
  • Example 1 A total heat exchange element paper of the present invention was obtained in the same manner as in Example 1 except that CM-CNF was not used. The adhesion amount, the air resistance, and the moisture permeability of this paper were measured. The results are shown in Table 1.
  • the base paper had a thin paper thickness due to densification by calendering, and the air resistance was high. However, the density, thickness, and air resistance were calendered by the wet and dry action during the coating process. Returning to the previous state, the paper thickness was thick and the air resistance was low.
  • ⁇ Comparative example 2> A total heat exchange element paper was obtained in the same manner as in Example 1 except that calcium chloride was not added and the amount of CM-CNF adhered was 0.3 g / m 2 . The adhesion amount, the air resistance, and the moisture permeability of this paper were measured. The results are shown in Table 1.
  • the amount of moisture absorbent applied to this paper was 2.5 g / m 2 in terms of solid content, and the amount of polyvinyl alcohol applied was 3.5 g / m 2 in terms of solid content.
  • the air permeation resistance was 23000 seconds, and the water vapor transmission rate was 1200 g / m 2 ⁇ 24 hr, and had sufficient air shielding and moisture permeability as a total heat exchange element paper.
  • the paper was subjected to a forced pressure bonding test using a hot-pressing roll in the same manner as in the evaluation of the blocking property, and the peel resistance was measured. As a result, the peel resistance was as extremely high as 300 g / cm or more, and part of the mother was not peeled off. Since the material was broken, it was evaluated that the blocking property was very strong.

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Abstract

Le problème abordé par la présente invention est de fournir du papier pour un élément de ventilation à récupération d'énergie qui peut être produit efficacement pendant la fabrication de papier, dans lequel des problèmes tels que le papier déchiré ne surviennent pas aisément pendant le traitement d'élément, et qui présente des propriétés d'absorption et de désorption d'humidité élevées et de protection contre l'air. Afin de résoudre le problème, l'invention concerne du papier pour un élément de ventilation à récupération d'énergie qui comprend une fibre pour fabrication de papier, un absorbant d'humidité et une nanofibre de cellulose.
PCT/JP2017/021890 2016-06-28 2017-06-14 Papier pour élément de ventilation à récupération d'énergie Ceased WO2018003492A1 (fr)

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WO2019151211A1 (fr) * 2018-01-31 2019-08-08 王子ホールディングス株式会社 Papier de base pour élément d'échangeur de chaleur total
JP2020020060A (ja) * 2018-08-01 2020-02-06 王子ホールディングス株式会社 シート
JP2020125893A (ja) * 2019-02-06 2020-08-20 王子ホールディングス株式会社 全熱交換器用シート、全熱交換器用素子、及び全熱交換器
CN111918999A (zh) * 2018-03-30 2020-11-10 日本制纸株式会社 羧甲基化微原纤化纤维素纤维和其组合物
JP2021155865A (ja) * 2020-03-26 2021-10-07 日本製紙パピリア株式会社 全熱交換素子用紙
JP2022507407A (ja) * 2018-11-14 2022-01-18 ストラ エンソ オーワイジェイ 表面処理組成物
US11466405B2 (en) 2018-03-30 2022-10-11 Nippon Paper Industries Co., Ltd. Carboxymethylated microfibrillated cellulose fibers and composition thereof

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