JP2016029226A - Base paper for total heat exchanger element and production method of the same - Google Patents
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- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
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- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
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Abstract
Description
本発明は、新鮮な外気を供給するとともに、室内の汚れた空気を排出する際に、顕熱（温度）と潜熱（湿度）の両方の熱交換を行う全熱交換器のエレメント用原紙に関する。 The present invention relates to a base paper for an element of a total heat exchanger that supplies fresh outside air and performs heat exchange of both sensible heat (temperature) and latent heat (humidity) when exhausting dirty air in a room.
従来、冷房や暖房の効果を損なわずに換気できる装置として、換気の際に給気と排気との間で熱交換をさせる熱交換換気装置（熱交換器）が提案されている。この熱交換器としては、スペーサーを介して複数の仕切り板（ライナー）を積層させ、室外の空気を室内に導入する給気経路と、室内の空気を室外に排出する排気経路とが区画されている全熱交換器エレメント（以下エレメントともいう）を有するものが広く採用されている。新鮮な外気を供給すると共に、室内の汚れた空気を排出する際に熱交換を行う空気対空気の熱交換器において、顕熱（温度）と同時に潜熱（湿度）の熱交換を行う全熱交換器エレメントのライナー部分は、伝熱性と透湿度の両方を有する必要があるため、多くの場合、天然パルプを主成分とする紙が用いられている。さらに、全熱交換器エレメントに使用する原紙、特にライナー部に使用する原紙としては、伝熱性と透湿度以外にも、高い耐熱性（防炎性）、及び、該ライナーを介して給気と排気が交じり合わないよう、ガスバリア性（主としてＣＯ２バリア性）が求められている。 2. Description of the Related Art Conventionally, a heat exchange ventilator (heat exchanger) that exchanges heat between air supply and exhaust during ventilation has been proposed as a device that can ventilate without impairing the effects of cooling and heating. As this heat exchanger, a plurality of partition plates (liners) are stacked via a spacer, and an air supply path for introducing outdoor air into the room and an exhaust path for discharging indoor air to the outside are partitioned. Those having a total heat exchanger element (hereinafter also referred to as an element) are widely adopted. Total heat exchange that supplies sensible heat (temperature) and latent heat (humidity) in an air-to-air heat exchanger that supplies fresh outside air and performs heat exchange when exhausting indoor dirty air Since the liner portion of the container element needs to have both heat conductivity and moisture permeability, paper mainly composed of natural pulp is used in many cases. Furthermore, as the base paper used for the total heat exchanger element, particularly the base paper used for the liner portion, in addition to heat transfer and moisture permeability, high heat resistance (flame resistance) and air supply through the liner Gas barrier properties (mainly CO 2 barrier properties) are required so that exhaust gases do not mix.
ライナー部は潜熱の熱交換を行うために空気中の水分を捕獲することにより水分量が変化するため、特にカビの増殖が問題となる。一般に低水分を好むカビとしては、ペニシリウム（青カビ）やアスペルギルス（コウジカビ）があり、高水分を好むものとしてはクラドスポリウム（黒カビ）等が挙げられる。
全熱交換器エレメント用原紙に防カビ性を付与する方法としては、ライナー部に無機系吸湿剤と無機系多孔質材と光触媒を含有させるものが提案されている（特許文献１）。この場合、ライナー部に光があたらない場合は、光触媒が機能しないため、防カビ効果を得ることが困難となる。
また、空気の流通経路とライナーのうち少なくとも一方に気化性防カビ剤を含有させるものが提案されている（特許文献２）。この場合は、防カビ剤を空気中に放散させるため、経時的に防カビ効果は損なわれてしまうため、長期間にわたる防カビ効果を得ることは困難と考えられる。
さらには、エレメントを構成するスペーサーとライナーとを接着する接着剤の中に防カビ剤を配合させる、あるいはエレメントの外側に防カビ剤を塗布する方法が提案されている（特許文献３）。この場合も最もカビが生育し易いライナー部すべてに対して防カビ処理を行うことは困難であり、十分な防カビ効果は得られにくく、満足な防カビ性を備えた全熱交換器エレメント用原紙は得られていないのが現状である。
Since the liner portion changes the amount of moisture by capturing moisture in the air in order to perform heat exchange of latent heat, the growth of mold is particularly problematic. In general, molds that prefer low moisture include penicillium (blue mold) and Aspergillus (koji mold), and those that prefer high moisture include cladosporium (black mold).
As a method for imparting antifungal properties to the base paper for a total heat exchanger element, a method in which an inorganic moisture absorbent, an inorganic porous material, and a photocatalyst are contained in a liner portion has been proposed (Patent Document 1). In this case, when the liner portion is not exposed to light, the photocatalyst does not function, so that it is difficult to obtain the antifungal effect.
Moreover, what makes a vaporizable antifungal agent contain in at least one among the distribution route of air and a liner is proposed (patent document 2). In this case, since the antifungal agent is diffused into the air, the antifungal effect is lost over time, and it is considered difficult to obtain the antifungal effect over a long period of time.
Furthermore, there has been proposed a method in which a fungicide is blended in an adhesive that bonds a spacer and a liner constituting the element, or a fungicide is applied to the outside of the element (Patent Document 3). Even in this case, it is difficult to perform mold prevention treatment on all liner parts where mold grows most easily, and it is difficult to obtain a sufficient mold prevention effect. For total heat exchanger elements with satisfactory mold resistance At present, the base paper is not available.
本発明は、高い全熱交換効率と長期間にわたる高い防カビ性能を兼ね備えた全熱交換器エレメント用原紙を提供することを目的とする。 An object of the present invention is to provide a base paper for a total heat exchanger element that has a high total heat exchange efficiency and a high antifungal performance over a long period of time.
本発明者らは、上記課題を解決するため鋭意研究を重ねた結果、以下の全熱交換器エレメント用原紙を開発するに至った。
即ち、本発明は以下のような各発明を包含する。
（１）パルプを主体とする紙基材からなり、吸湿率が１５〜３０％であり、且つ前記紙基材中に疎水性有機化合物である防カビ剤を含有する全熱交換器エレメント用原紙。
As a result of intensive studies to solve the above problems, the present inventors have developed the following base paper for a total heat exchanger element.
That is, the present invention includes the following inventions.
(1) A base paper for a total heat exchanger element comprising a paper base mainly composed of pulp, having a moisture absorption rate of 15 to 30%, and containing a fungicidal agent which is a hydrophobic organic compound in the paper base. .
（２）前記防カビ剤が前記全熱交換器エレメント用原紙全体に対して０．０１〜５．０質量％含有する（１）に記載の全熱交換器エレメント用原紙。 (2) The base paper for total heat exchanger elements according to (1), wherein the antifungal agent is contained in an amount of 0.01 to 5.0% by mass with respect to the total base paper for total heat exchanger elements.
（３）前記防カビ剤が、ベンズイミダゾール系化合物またはピリチオン系化合物である（１）または（２）に記載の全熱交換器エレメント用原紙。 (3) The base paper for a total heat exchanger element according to (1) or (2), wherein the antifungal agent is a benzimidazole compound or a pyrithione compound.
本発明により、高い全熱交換効率と長期間にわたる高い防カビ性能を有する全熱交換器エレメント用原紙を得ることができる。 According to the present invention, it is possible to obtain a base paper for a total heat exchanger element having high total heat exchange efficiency and high anti-mold performance over a long period of time.
本発明の全熱交換器エレメント用原紙（以下、エレメント用原紙とも言う）の原料として使用するパルプは、針葉樹パルプ、広葉樹パルプでもよく、蒸解方法や漂白方法は特に限定されない。ただし、原紙の強度やＣＯ２バリア性の発現効果を考慮し、針葉樹晒クラフトパルプ（ＮＢＫＰ）を主原料として使用することが好ましい。また、木材パルプ以外にも、麻パルプやケナフ、竹などの非木材パルプが使用できると共に、レーヨン繊維やナイロン繊維、その他熱融着繊維など、パルプ繊維以外の材料も副資材として配合することが可能である。
抄造後にパーチメント処理を行うことによって、紙力やＣＯ２バリア性を得ることも可能である。
The pulp used as the raw material for the total heat exchanger element base paper (hereinafter also referred to as element base paper) of the present invention may be softwood pulp or hardwood pulp, and the cooking method and bleaching method are not particularly limited. However, it is preferable to use softwood bleached kraft pulp (NBKP) as the main raw material in consideration of the strength of the base paper and the expression effect of the CO 2 barrier property. In addition to wood pulp, non-wood pulp such as hemp pulp, kenaf, and bamboo can be used, and materials other than pulp fiber such as rayon fiber, nylon fiber, and other heat-sealing fibers can be added as auxiliary materials. Is possible.
It is also possible to obtain paper strength and CO 2 barrier properties by performing a parchment treatment after papermaking.
本発明で使用するパルプのフリーネスは、適宜選定可能であるが、原紙を薄葉化し、かつ、ＣＯ２バリア性を得るための高透気度を発現させるためには、基材紙を構成するパルプの変則フリーネス（本発明において、パルプ採取量を通常の３ｇ／Ｌから０．３ｇ／Ｌに変更した以外はＪＩＳ Ｐ ８１２１−２：２０１２に準じて測定したフリーネスを意味する）が、２００〜６００ｍｌの範囲にあることが好ましい。変則フリーネスが２００ｍｌ未満の場合は、実機操業での叩解に時間を要するとともに、抄紙時の脱水性が悪化するため、操業効率が低下してしまう。また、紙自体も脆くなりやすいという問題が発生するおそれがある。
逆に、変則フリーネスが６００ｍｌを超えると、薄葉化を維持しつつＣＯ２バリア性を発現することが困難になるという問題が発生するおそれがある。使用するパルプの実機での叩解方法、装置は特に限定されるものではないが、叩解効率が高いダブルディスクリファイナー（ＤＤＲ）が好適に使用される。
The freeness of the pulp used in the present invention can be selected as appropriate. However, in order to make the base paper thin and to exhibit high air permeability for obtaining CO 2 barrier properties, the pulp constituting the base paper is used. Anomalous freeness (in the present invention, the freeness measured according to JIS P 8121-2: 2012 except that the amount of collected pulp was changed from the usual 3 g / L to 0.3 g / L) was 200 to 600 ml. It is preferable that it exists in the range. When the irregular freeness is less than 200 ml, it takes time to beat the actual machine, and the dewaterability during paper making deteriorates, so that the operation efficiency is lowered. In addition, there is a risk that the paper itself is likely to become brittle.
On the other hand, if the irregular freeness exceeds 600 ml, there is a possibility that it may be difficult to develop a CO 2 barrier property while maintaining thinning. The beating method and apparatus of the pulp used in the actual machine are not particularly limited, but a double disc refiner (DDR) having high beating efficiency is preferably used.
上記叩解して得たパルプスラリーには、各種製紙用内添薬品を添加する。内添薬品としては、紙力増強剤、湿潤紙力増強剤、硫酸バンド、カチオン化デンプン等、各種定着剤が挙げられる。また、填料や着色剤などを任意に配合可能である。特に、エレメント用原紙は、吸湿性が高くなるので、強度保持の観点からも、湿潤紙力剤を配合することが好ましい。 Various internal chemicals for papermaking are added to the pulp slurry obtained by the beating. Examples of the internal additive include various fixing agents such as a paper strength enhancer, a wet paper strength enhancer, a sulfuric acid band, and a cationized starch. Moreover, a filler, a coloring agent, etc. can be arbitrarily mix | blended. In particular, since the element base paper has high hygroscopicity, it is preferable to add a wet paper strength agent from the viewpoint of maintaining strength.
このように調成したパルプスラリー原料を常法により抄紙することで、本発明のエレメント用原紙の基材紙を得る。本発明は、さらに吸湿剤を主成分とした薬液を基材紙に添加させて全熱交換器エレメント用原紙が得られる。薬液の基材紙への添加は、抄紙機のオンマシンサイズプレス装置やスプレー装置等を用いて行うことができる。また、オフマシンの含浸機によって浸漬することも可能である。操業性、生産性を考慮すれば、オンマシンでのサイズプレスによる添加が好ましい。従って、本発明の基材紙を抄紙する抄紙機の形式については、長網抄紙機、短網抄紙機、円網抄紙機等、特に限定されるものではないが、オンマシンでサイズプレス機、もしくは含浸機が装備されているものを用いることが好ましい。このような抄紙機を用いて薬液を添加させることにより、紙基材の全面において後述する防カビ剤を含有する全熱交換器エレメント用原紙を得ることができる。 The base material paper of the element base paper of the present invention is obtained by papermaking the pulp slurry raw material thus prepared by a conventional method. In the present invention, a base paper for a total heat exchanger element can be obtained by further adding a chemical solution mainly composed of a hygroscopic agent to the base paper. The chemical solution can be added to the base paper using an on-machine size press device or a spray device of a paper machine. It is also possible to immerse with an off-machine impregnation machine. In consideration of operability and productivity, addition by an on-machine size press is preferable. Accordingly, the type of paper machine for making the base paper of the present invention is not particularly limited, such as a long net paper machine, a short net paper machine, a circular net paper machine, etc., but an on-machine size press machine, Or it is preferable to use what is equipped with the impregnation machine. By adding a chemical solution using such a paper machine, it is possible to obtain a base paper for a total heat exchanger element containing a fungicide described later on the entire surface of the paper substrate.
薬液中に含有させる吸湿剤としては特に限定するものではないが、例えば塩化カルシウム、塩化リチウム等の水溶性塩類、尿素、カラギーナン、アルギン酸、アルギン酸塩等の保湿剤が挙げられ、なかでも塩化カルシウムが吸湿効果と経済性に優れているため好ましい。吸湿剤の付着量も特に限定するものではなく、例えば基材紙絶乾坪量に対し、５〜３０質量％の範囲、より好ましくは１０〜２５質量％程度の範囲で調整される。
吸湿剤の付着量が５質量％未満では、吸放湿性能が不十分となる。また、吸湿剤の付着量が３０質量％を超える場合は、結露を起こす可能性があり、全熱交換効率を損なうおそれがあるため好ましくない。
Although it does not specifically limit as a hygroscopic agent contained in a chemical | medical solution, For example, humectants, such as water-soluble salts, such as calcium chloride and lithium chloride, urea, carrageenan, alginic acid, alginate, etc. are mentioned. It is preferable because of its excellent moisture absorption effect and economical efficiency. The adhering amount of the hygroscopic agent is also not particularly limited, and for example, it is adjusted in the range of 5 to 30% by mass, more preferably in the range of about 10 to 25% by mass with respect to the base paper absolute dry basis weight.
If the amount of adsorbent of the hygroscopic agent is less than 5% by mass, the hygroscopic performance is insufficient. Moreover, when the adhering amount of the hygroscopic agent exceeds 30% by mass, there is a possibility of causing dew condensation, which is unfavorable because the total heat exchange efficiency may be impaired.
なお、抄紙設備によっては、塩化カルシウム等の塩類により錆が発生するおそれがあるため、塩化カルシウムの水溶液に水溶性の防錆剤を配合しておくことが好ましい。防錆剤としては、環境安全性を考慮し、脂肪族カルボン酸のナトリウム塩等の非亜硝酸系のものを選択するのが好ましい。また、塩化カルシウム水溶液に対する防錆剤の添加量は、特に限定はないが、薬液中の固形分含有率として、０．５〜１０質量％程度の範囲で調整される。 Depending on the papermaking equipment, rust may be generated by salts such as calcium chloride. Therefore, it is preferable to add a water-soluble rust preventive to an aqueous solution of calcium chloride. As the rust preventive agent, it is preferable to select a non-nitrite-based one such as a sodium salt of an aliphatic carboxylic acid in consideration of environmental safety. Moreover, the addition amount of the rust inhibitor with respect to the calcium chloride aqueous solution is not particularly limited, but is adjusted in the range of about 0.5 to 10% by mass as the solid content in the chemical solution.
また、基材紙の吸湿率は、１５〜３０％の範囲内でコントロールする必要がある。吸湿率が１５％未満では、熱交換効率が不十分となるが、吸湿率が３０％を超えると、結露や液ダレが発生するおそれがある。
なお、吸湿剤に塩化カルシウムを用いる場合、塩化カルシウムは吸湿性が高く、通常結晶水を保持しており、乾燥質量による付着量が算出しにくい。従って、塩化カルシウムの付着量は、塩化カルシウムの水溶液のウェット付着量に、塩化カルシウムの無水物としての濃度を乗じたものである。塩化カルシウム水溶液における塩化カルシウム（無水物）の濃度は、ＥＤＴＡ滴定法により求めることができる。
Moreover, it is necessary to control the moisture absorption rate of the base paper within a range of 15 to 30%. If the moisture absorption rate is less than 15%, the heat exchange efficiency is insufficient, but if the moisture absorption rate exceeds 30%, condensation or dripping may occur.
When calcium chloride is used as the hygroscopic agent, calcium chloride has high hygroscopicity and usually retains water of crystallization, making it difficult to calculate the amount of adhesion due to dry mass. Therefore, the adhesion amount of calcium chloride is obtained by multiplying the wet adhesion amount of the aqueous solution of calcium chloride by the concentration of calcium chloride as an anhydride. The concentration of calcium chloride (anhydride) in the aqueous calcium chloride solution can be determined by the EDTA titration method.
薬液には必要に応じて難燃剤を添加することも可能である。難燃剤としては特に限定するものではないが、本発明では例えば、リン酸グアニジン、スルファミン酸グアニジン等の脱水により難燃性が得られる化合物が好ましい。 A flame retardant may be added to the chemical liquid as necessary. Although it does not specifically limit as a flame retardant, In this invention, the compound which can obtain a flame retardance by dehydration, such as guanidine phosphate and guanidine sulfamate, is preferable.
エレメント用原紙の吸放湿性、熱交換効率の指標としては、透湿度が有効であり、透湿度が高い方が、概して熱交換効率が高い。本発明のエレメント用原紙は、温度２０℃、湿度６５％ＲＨ環境下での透湿度（ＪＩＳ Ｚ ０２０８：１９７６「防湿包装材料の透湿度試験方法（カップ法）」に準ずる。詳細は実施例の測定方法参照。）が２０００ｇ／ｍ２・２４ｈｒ以上を達成可能である。 Moisture permeability is effective as an index of moisture absorption / release characteristics and heat exchange efficiency of element base paper, and heat exchange efficiency is generally higher when moisture permeability is higher. The element base paper of the present invention conforms to moisture permeability (JIS Z 0208: 1976 “moisture-proof packaging material moisture permeability test method (cup method)” at a temperature of 20 ° C. and a humidity of 65% RH. Can be 2000 g / m 2 · 24 hr or more.
また、基材紙に吸湿剤を添加することで、紙の保水性が高くなるため、巻き取り時のブロッキングの防止や、各工程におけるロール剥離性を考慮し、ブロッキング防止剤も添加することが望ましい。ブロッキング防止剤としては特に限定するものではないが、例えばポリエチレン系ワックス、ステアリン酸亜鉛、ポリエチレン系ワックス乳化物、酸化ポリエチレン系ワックス、パラフィンワックスなどから選ばれたワックス類、シリコーン系樹脂や高級脂肪酸カルシウム塩などの金属石鹸類等の中から選ばれる。ブロッキング防止剤の添加については、塗工、含浸、噴霧等、常法より適宜選択可能である。また、抄紙機のオンマシンによるサイズプレスにより行うことが生産性の点から好適である。ブロッキング防止剤の添加量には特に限定はないが、例えば、薬液に対して０．０１〜０．５質量％程度加えることが好ましい。０．０１質量％未満では十分な効果が得られないおそれがあり、０．５質量％を超えた場合は、ペーパーロールやカレンダーロール上に付着したり、後工程の加工時に滑りトラブルが発生するおそれがあるため好ましくない。 Also, by adding a hygroscopic agent to the base paper, the water retention of the paper is increased, so that blocking prevention at the time of winding and roll releasability in each step can be considered, and an anti-blocking agent can also be added. desirable. The anti-blocking agent is not particularly limited. For example, waxes selected from polyethylene wax, zinc stearate, polyethylene wax emulsion, polyethylene oxide wax, paraffin wax, silicone resin, and higher fatty acid calcium. Selected from metal soaps such as salt. About addition of an antiblocking agent, it can select suitably from a conventional method, such as coating, an impregnation, and spraying. Moreover, it is suitable from the point of productivity to carry out by the size press by the on-machine of a paper machine. Although there is no limitation in the addition amount of an antiblocking agent, For example, it is preferable to add about 0.01-0.5 mass% with respect to a chemical | medical solution. If it is less than 0.01% by mass, a sufficient effect may not be obtained. If it exceeds 0.5% by mass, it may adhere to a paper roll or a calender roll, or a slipping trouble may occur during processing in a subsequent process. This is not preferable because of fear.
本発明の全熱交換器エレメント用原紙は、その基材紙中に疎水性有機化合物である防カビ剤を含有させるものである。本実施形態においては、上記防カビ剤として、エマルション型防カビ剤を使用することができる。エマルション型防カビ剤は疎水性物質の水性分散物であるため、基材紙に塗布または含浸させた後は基材紙中に定着する。したがって、空気中の水分には再溶解しにくく、長期間にわたって防カビ効果を発現すると考えられ、全熱交換器エレメント用原紙に特に好適である。
水溶性の防カビ剤では、高水分になった場合に流れ出て効果が失われるおそれがある。また、無機粒子粉末の防カビ剤については、一般に比重が大きいため、含浸やサイズプレス塗工等の方法では基材紙中に保持させることが難しく、全熱交換器エレメント用原紙には適していない。
The base paper for a total heat exchanger element of the present invention contains an antifungal agent which is a hydrophobic organic compound in the base paper. In the present embodiment, an emulsion type antifungal agent can be used as the antifungal agent. Since the emulsion type antifungal agent is an aqueous dispersion of a hydrophobic substance, it is fixed in the base paper after being applied or impregnated on the base paper. Therefore, it is difficult to re-dissolve in moisture in the air, and it is considered that the anti-mold effect is exhibited over a long period of time, and is particularly suitable for the base paper for the total heat exchanger element.
In the case of water-soluble fungicides, there is a risk that the effect will be lost by flowing out when the moisture becomes high. In addition, the antifungal agent of the inorganic particle powder generally has a large specific gravity, so it is difficult to hold it in the base paper by impregnation or size press coating, and is suitable for the base paper for the total heat exchanger element. Absent.
本発明では疎水性有機化合物である防カビ剤の全熱交換器エレメント用原紙全体に対する含有率は特に限定するものではないが、例えば０．０１〜５．０質量％、より好ましくは０．１〜３．０質量％程度の範囲で調整される。含有率が０．０１質量％未満の場合は満足な防カビ性能が得られない。また、５．０質量％を超える場合は、防カビ性能に対して過剰量となり経済的に好ましくない。なお、防カビ剤の含有率は、たとえば元素分析や赤外分光法により化合物の構造を特定した後、定量分析を行うことにより測定することが可能である。 In the present invention, the content of the fungicide, which is a hydrophobic organic compound, with respect to the entire base paper for the total heat exchanger element is not particularly limited, but is, for example, 0.01 to 5.0% by mass, more preferably 0.1%. It is adjusted in the range of about ~ 3.0% by mass. When the content is less than 0.01% by mass, satisfactory antifungal performance cannot be obtained. Moreover, when it exceeds 5.0 mass%, it becomes an excessive amount with respect to mold prevention performance, and is not economically preferable. The content of the fungicide can be measured, for example, by specifying the structure of the compound by elemental analysis or infrared spectroscopy and then performing quantitative analysis.
防カビ剤の種類としては特に限定するものではないが、例えばベンズイミダゾール系化合物、ピリチオン系化合物、ヨードプロペニルブチルカルバメート系化合物、イソチアゾロン系化合物、有機窒素硫黄系化合物等のエマルションが挙げられる。また、２種以上を併用することも可能である。
なかでもベンズイミダゾール系、ピリチオン系の化合物が防カビ性の面で好ましく、さらにピリチオン系の化合物が安全性も高いため最も好ましい。
Although it does not specifically limit as a kind of anti-mold agent, For example, emulsions, such as a benzimidazole type compound, a pyrithione type compound, an iodopropenyl butyl carbamate type compound, an isothiazolone type compound, an organic nitrogen sulfur type compound, are mentioned. Two or more kinds can be used in combination.
Of these, benzimidazole-based and pyrithione-based compounds are preferable in terms of antifungal properties, and pyrithione-based compounds are most preferable because of their high safety.
本発明において、防カビ剤の添加方法としては、吸湿剤を主成分とする薬液中に添加して、オンマシンでサイズプレス、もしくは含浸させることが好ましい。 In the present invention, as a method for adding the antifungal agent, it is preferable to add it to a chemical solution containing a hygroscopic agent as a main component, and size press or impregnate it on-machine.
本発明では、その効果を損なわない範囲において他の防カビ剤を併用することも可能である。例えば、上記エマルション型防カビ剤と同様の成分で水溶性のもの、銀をリン酸ジルコニウムに担持させたもの、無機層状化合物に有機物を担持させたもの等が挙げられる。 In the present invention, other fungicides can be used in combination as long as the effect is not impaired. For example, the same components as the above-mentioned emulsion type antifungal agent, water-soluble, those in which silver is supported on zirconium phosphate, and those in which an organic substance is supported on an inorganic layered compound.
本発明においては、基材紙にＰＶＡやデンプン、ＳＢＲ等のラテックス類やアクリル系樹脂等の高分子樹脂を塗工や含浸等の手段により添加することで、さらにガスバリア性の向上を図ることができる。なお、ガスバリア性向上のために添加する高分子樹脂としては、ＰＶＡがＣＯ２バリア性に特に有効なため好適に利用可能である。高分子樹脂の添加方法としては、常法より適宜選択可能であるが、吸湿剤の添加と同様、抄紙機のオンマシンによるサイズプレスにより行うことが好適である。
なお、薬液にはポリアクリルアミド等の紙力剤、さらにはポリアミドポリアミンエピクロルヒドリン化合物等の湿潤紙力剤等を添加することも可能である。
In the present invention, the gas barrier property can be further improved by adding latex resins such as PVA, starch and SBR, and polymer resins such as acrylic resins to the base paper by means of coating or impregnation. it can. As the polymer resin added for improving the gas barrier property, PVA can be suitably used because it is particularly effective for the CO 2 barrier property. The addition method of the polymer resin can be appropriately selected from conventional methods, but it is preferable to carry out by a size press by an on-machine of the paper machine, as in the case of adding the moisture absorbent.
In addition, it is also possible to add a paper strength agent such as polyacrylamide and a wet strength agent such as a polyamide polyamine epichlorohydrin compound to the chemical solution.
本発明の全熱交換器エレメント用原紙は、前述の通り、基材紙に薬液を添加した後、さらにカレンダー処理を施して得ることが好適である。カレンダー処理を施すことによって、原紙が高密度となると同時に厚さが減少する。高密度となることによって、ガスバリア性が向上し、また厚さが減少することによって熱伝導率が上昇し、熱交換効率が上昇するという効果が得られる。本発明のエレメント用原紙の密度は特に限定するものではないが、ガスバリア性の観点からは、０．９〜１．２ｇ／ｃｍ３の範囲であることが好ましい。なお、パーチメント等、他の方法でガスバリア性を高める場合はこの限りではない。 As described above, the base paper for a total heat exchanger element of the present invention is preferably obtained by adding a chemical solution to the base paper and further subjecting it to a calender treatment. By applying the calendering process, the base paper becomes dense and at the same time the thickness decreases. By increasing the density, the gas barrier property is improved, and by reducing the thickness, the thermal conductivity is increased and the heat exchange efficiency is increased. The density of the element base paper of the present invention is not particularly limited, but is preferably in the range of 0.9 to 1.2 g / cm 3 from the viewpoint of gas barrier properties. However, this is not the case when the gas barrier property is enhanced by other methods such as parchment.
また、熱伝導率の観点から、厚さが薄いものほど好ましく、具体的には厚さ７０μｍ以下とすることがより好ましい。なお、全熱交換器エレメント用原紙は、所定のガスバリア性を有する前提であれば、低坪量であるほど好ましく、具体的には坪量７０ｇ／ｍ２以下であることがより好ましい。全熱交換器エレメント用原紙の低坪量化、薄葉化は、エレメントの軽量化や、同サイズでのエレメントの積層段数の増加を可能にするため、熱交換効率の向上にも有効である。 Further, from the viewpoint of thermal conductivity, a thinner one is preferable, and specifically, a thickness of 70 μm or less is more preferable. In addition, if the base paper for total heat exchanger elements is a premise which has predetermined | prescribed gas barrier property, it is so preferable that it is a low basic weight, and it is more preferable that the basic weight is 70 g / m < 2 > or less specifically. Lowering the basis weight and thinning of the base paper for the total heat exchanger element enables the weight reduction of the element and the increase in the number of stacked layers of the element at the same size, which is effective in improving the heat exchange efficiency.
なお、本発明においては、全熱交換器エレメント用原紙に高いガスバリア性を付与するため、前述のカレンダー処理後に、後加工としてさらにＰＶＡ等の高分子樹脂を塗工することも可能である。この場合、紙基材の少なくとも表面に、高分子樹脂により構成される樹脂層が形成されることとなる。 In addition, in this invention, in order to provide a high gas barrier property to the base paper for total heat exchanger elements, it is also possible to apply a polymer resin such as PVA as a post-processing after the above calendering. In this case, a resin layer composed of a polymer resin is formed on at least the surface of the paper substrate.
全熱交換器エレメント用原紙においては、吸気と排気を混合させないため、十分なガスバリア性を有する必要がある。ガスバリア性の中でも特にＣＯ２バリア性が重要である。ガスバリア性とは透気度（ＪＡＰＡＮ ＴＡＰＰＩ 紙パルプ試験方法Ｎｏ．５−２：２０００の王研式透気度法）で表現することが可能であり、透気度が５０００秒以上であることが好ましい。
全熱交換器エレメント用原紙は、とくに限定されないが、たとえばロール状に巻き取られている。これにより、搬送に供する際等における取扱い性を向上させることができる。また、全熱交換器エレメント用原紙は、たとえば全熱交換器エレメントを構成するスペーサーまたはライナーを形成するために用いられ、とくにライナーを形成するために好適に用いることができる。本実施形態は、このように上述の全熱交換器エレメント用原紙を用いて形成されたライナーを備える全熱交換器エレメントを実現し得るものである。
In the base paper for the total heat exchanger element, it is necessary to have a sufficient gas barrier property in order not to mix intake and exhaust. Among the gas barrier properties, the CO2 barrier property is particularly important. The gas barrier property can be expressed by air permeability (JAPAN TAPPI paper pulp test method No. 5-2: 2000 Oken air permeability method), and the air permeability is 5000 seconds or more. preferable.
Although the base paper for total heat exchanger elements is not particularly limited, it is wound into a roll, for example. Thereby, the handleability in the case of using for conveyance etc. can be improved. Further, the base paper for the total heat exchanger element is used, for example, to form a spacer or a liner constituting the total heat exchanger element, and can be suitably used particularly for forming a liner. In this embodiment, a total heat exchanger element including a liner formed using the above-described total heat exchanger element base paper can be realized.
以下実施例により本発明をさらに詳しく説明する。なお、実施例及び比較例における％、部は、特に断りのない限り質量％、質量部を表す。 Hereinafter, the present invention will be described in more detail with reference to examples. In addition,% and a part in an Example and a comparative example represent the mass% and a mass part unless there is particular notice.
＜実施例１＞
針葉樹晒クラフトパルプ（ＮＢＫＰ）８０％と広葉樹晒クラフトパルプ（ＬＢＫＰ）２０％を混合し、ＤＤＲにて、変則フリーネス（パルプ採取量０．３ｇ／Ｌ）が４５０ｍｌとなるように叩解した。内添薬品としては、パルプ質量に対し、絶乾でポリアクリルアミド系紙力剤（商品名：「ポリストロン１１７」、荒川化学工業社製）０．５％、ポリアミドポリアミンエピクロルヒドリン系湿潤紙力剤（商品名：「アラフィックス２５５」、荒川化学工業社製）０．５％、硫酸バンド０．５％を添加した。上記で得た原料を長網抄紙機で抄紙し、マングル含浸機により下記吸湿剤を主成分とする薬液を含浸付着させて乾燥させたものを基材紙とし、該基材紙をスーパーカレンダー処理して本発明の全熱交換器エレメント用原紙を得た。なお、上記の基材紙の坪量は絶乾で４０ｇ／ｍ２、吸湿剤（塩化カルシウム）の付着量は、無水塩化カルシウム換算で４．５ｇ／ｍ２であった。また、全熱交換器エレメント用原紙全体に対する防カビ剤の含有率は、０．５６質量％であった。
<Example 1>
80% of softwood bleached kraft pulp (NBKP) and 20% of hardwood bleached kraft pulp (LBKP) were mixed and beaten with DDR so that the irregular freeness (pulp collection amount 0.3 g / L) was 450 ml. As internal additives, the polyacrylamide-based paper strength agent (trade name: “Polystron 117”, manufactured by Arakawa Chemical Industry Co., Ltd.) 0.5%, polyamide polyamine epichlorohydrin-based wet paper strength agent (based on the mass of the pulp) Trade name: “Arafix 255” (manufactured by Arakawa Chemical Industries, Ltd.) 0.5% and sulfuric acid band 0.5% were added. The raw material obtained above is made with a long paper machine, impregnated with a chemical solution mainly composed of the following hygroscopic agent with a mangle impregnator and dried, and the base paper is used as a base calendar paper. Thus, a base paper for a total heat exchanger element of the present invention was obtained. The basis weight of the base paper was 40 g / m 2 when it was absolutely dry, and the amount of moisture absorbent (calcium chloride) deposited was 4.5 g / m 2 in terms of anhydrous calcium chloride. Moreover, the content rate of the antifungal agent with respect to the whole base paper for total heat exchanger elements was 0.56 mass%.
［吸湿剤を主成分とする薬液］
塩化カルシウム（吸湿剤：セントラル硝子社製）：８９％（無水物換算固形分含有率）、脂肪族カルボン酸ナトリウム塩系防錆剤（商品名：「メタレックスＡＮＫ」、油化産業社製）５．９８％（固形分含有率）、ポリエチレン系ブロッキング防止剤（商品名：「ノプコートＰＥＭ−１７」、サンノプコ社製）０．０２％（固形分含有率）、ピリチオン系エマルション型防カビ剤（商品名：「アモルデンＮ−７１８」、大和化学社製）５％（固形分含有率）を配合し、上記の成分の薬液を薬液濃度２０％で調製した。
[Chemical solution mainly composed of hygroscopic agent]
Calcium chloride (hygroscopic agent: manufactured by Central Glass Co., Ltd.): 89% (anhydrous equivalent solid content), aliphatic carboxylic acid sodium salt-based rust preventive (trade name: “Metalex ANK”, manufactured by Yuka Sangyo Co., Ltd.) 5.98% (solid content), polyethylene antiblocking agent (trade name: “Nopcoat PEM-17”, manufactured by San Nopco) 0.02% (solid content), pyrithione emulsion type antifungal agent ( Product name: “Amorden N-718” (manufactured by Daiwa Chemical Co., Ltd.) 5% (solid content) was blended, and a chemical solution of the above components was prepared at a chemical concentration of 20%.
＜実施例２＞
実施例１の薬液調製において、防カビ剤の固形分含有率を２．５％とし、且つ塩化カルシウムの固形分含有率を９１．５％とした以外は実施例１と同様にして本発明の全熱交換器エレメント用原紙を得た。また、全熱交換器エレメント用原紙全体に対する防カビ剤の含有率は、０．２７質量％であった。
<Example 2>
In the preparation of the chemical solution of Example 1, the solid content of the fungicide was 2.5%, and the solid content of calcium chloride was 91.5%. A base paper for a total heat exchanger element was obtained. Moreover, the content rate of the fungicide with respect to the whole base paper for total heat exchanger elements was 0.27 mass%.
＜実施例３＞
実施例１の薬液調製において、防カビ剤の固形分含有率を２４％とし、且つ塩化カルシウムの固形分含有率を７０％とした以外は実施例１と同様にして本発明の全熱交換器エレメント用原紙を得た。また、全熱交換器エレメント用原紙全体に対する防カビ剤の含有率は、３．３質量％であった。
<Example 3>
In the preparation of the chemical solution of Example 1, the total heat exchanger of the present invention was the same as Example 1 except that the solid content of the fungicide was 24% and the solid content of calcium chloride was 70%. Element base paper was obtained. Moreover, the content rate of the antifungal agent with respect to the whole base paper for total heat exchanger elements was 3.3 mass%.
＜実施例４＞
実施例１の薬液調製において、ピリチオン系エマルション型防カビ剤の替わりにベンズイミダゾール系エマルション型防カビ剤（商品名：「アモルデンＮ−７８２０」、大和化学社製）を固形分含有率５％使用した以外は実施例１と同様にして本発明の全熱交換器エレメント用原紙を得た。また、全熱交換器エレメント用原紙全体に対する防カビ剤の含有率は、０．５６質量％であった。
<Example 4>
In the preparation of the chemical solution of Example 1, a benzimidazole emulsion type antifungal agent (trade name: “Amorden N-7820”, manufactured by Daiwa Chemical Co., Ltd.) is used instead of the pyrithione emulsion type antifungal agent. Except that, a base paper for a total heat exchanger element of the present invention was obtained in the same manner as in Example 1. Moreover, the content rate of the antifungal agent with respect to the whole base paper for total heat exchanger elements was 0.56 mass%.
＜比較例１＞
実施例１の薬液調製において、防カビ剤を添加せず、且つ塩化カルシウムの固形分含有率を９４％とした以外は実施例１と同様にしてエレメント用原紙を得た。
<Comparative Example 1>
An element base paper was obtained in the same manner as in Example 1 except that the antifungal agent was not added and the solid content of calcium chloride was 94% in the preparation of the chemical solution of Example 1.
＜比較例２＞
実施例４の薬液調製において、ベンズイミダゾール系エマルション型防カビ剤の替わりに、ベンズイミダゾール系水溶性防カビ剤（商品名：「アモルデンＨＳ」、大和化学社製）を固形分含有率５％使用した以外は実施例４と同様にしてエレメント用原紙を得た。また、全熱交換器エレメント用原紙全体に対する防カビ剤の含有率は、０．５６質量％であった。
<Comparative Example 2>
In the preparation of the chemical solution of Example 4, instead of the benzimidazole emulsion type antifungal agent, a benzimidazole water-soluble antifungal agent (trade name: “Amorden HS”, manufactured by Daiwa Chemical Co., Ltd.) is used at a solid content of 5%. An element base paper was obtained in the same manner as in Example 4 except that. Moreover, the content rate of the antifungal agent with respect to the whole base paper for total heat exchanger elements was 0.56 mass%.
＜比較例３＞
実施例１の薬液調製において、ピリチオン系エマルション型防カビ剤の替わりにヨードプロペニルブチルカルバメート系水溶性防カビ剤（商品名：「アモルデンＴＩＰ−０５」、大和化学社製）を固形分含有率５％使用した以外は実施例１と同様にしてエレメント用原紙を得た。また、全熱交換器エレメント用原紙全体に対する防カビ剤の含有率は、０．５６質量％であった。
<Comparative Example 3>
In the preparation of the chemical solution of Example 1, an iodopropenyl butyl carbamate water-soluble antifungal agent (trade name: “Amorden TIP-05”, manufactured by Daiwa Chemical Co., Ltd.) was used instead of the pyrithione emulsion type antifungal agent. Element base paper was obtained in the same manner as in Example 1 except that% was used. Moreover, the content rate of the antifungal agent with respect to the whole base paper for total heat exchanger elements was 0.56 mass%.
＜比較例４＞
実施例１の薬液調製において、ピリチオン系エマルション型防カビ剤の替わりに銀をリン酸ジルコニウムに担持させた水不溶性粉末（商品名：「ノバロンＡＧ１１００」、東亞合成社製）を固形分含有率５％使用した以外は実施例１と同様にしてエレメント用原紙を得た。また、全熱交換器エレメント用原紙全体に対する防カビ剤の含有率は、０．５６質量％であった。
<Comparative example 4>
In the preparation of the chemical solution of Example 1, a water-insoluble powder (trade name: “NOVALON AG1100”, manufactured by Toagosei Co., Ltd.) in which silver is supported on zirconium phosphate instead of the pyrithione emulsion type antifungal agent has a solid content of 5 Element base paper was obtained in the same manner as in Example 1 except that% was used. Moreover, the content rate of the antifungal agent with respect to the whole base paper for total heat exchanger elements was 0.56 mass%.
実施例、比較例で得た各エレメント用原紙を試料として下記の方法で評価した。その結果を表１に示す。 Each element base paper obtained in Examples and Comparative Examples was used as a sample and evaluated by the following method. The results are shown in Table 1.
［評価方法］
＜透湿度＞
２０℃×６５％ＲＨの条件下で、ＪＩＳ Ｚ ０２０８：１９７６「防湿包装材料の透湿度試験方法（カップ法）」に準拠して測定する。
但し、下記式により算出。
透湿度＝（ａ＋ｂ）／２
ａ＝測定開始１時間後の質量増分
ｂ＝測定開始１時間後から測定開始２時間後の１時間の質量増分
[Evaluation method]
<Moisture permeability>
Measurement is performed in accordance with JIS Z 0208: 1976 “Moisture permeability test method for moisture-proof packaging material (cup method)” under the condition of 20 ° C. × 65% RH.
However, calculated by the following formula.
Moisture permeability = (a + b) / 2
a = mass increment 1 hour after start of measurement b = mass increment 1 hour after start of measurement 2 hours after start of measurement
＜吸湿率＞
下記式で算出する。
吸湿率＝｛（Ａ−Ｂ）／Ｂ｝×１００
Ａ＝試料質量（２０℃×６５％ＲＨの条件下の質量）
Ｂ＝試料絶乾質量（１０５℃のオーブンで２時間加熱乾燥後の質量）
<Hygroscopic rate>
Calculate with the following formula.
Moisture absorption rate = {(A−B) / B} × 100
A = Sample mass (mass under the condition of 20 ° C. × 65% RH)
B = Sample dry mass (mass after being heated and dried in an oven at 105 ° C. for 2 hours)
＜透気度＞
ＪＡＰＡＮ ＴＡＰＰＩ 紙パルプ試験方法Ｎｏ．５−２：２０００の王研式透気度法に準拠して測定する。
<Air permeability>
JAPAN TAPPI Paper Pulp Test Method No. 5-2: Measured according to the 2000 Oken air permeability method.
＜防カビ性＞
ＪＩＳ Ｚ ２９１１：２０１０の「かび抵抗性試験方法（湿式法）」に準拠して評価する。ただし、流水による前処理は実施しない。試験期間：１週間、２週間、４週間。
供試菌：ＪＩＳ Ｚ ２９１１中の第１群アスペルギルスニゲル、第２群ペニシリウムシトリナム、第４群クラドスポリウムクラドスポリオイデス、第５群ケトミウムグロボスム。
（防カビ性の評価基準）
０：試料又は試験片の接種した部分に菌糸の発育が認められない。
１：試料又は試験片の接種した部分に認められる菌糸の発育部分の面積は、全面積の１／３を超えない。
２：試料又は試験片の接種した部分に認められる菌糸の発育部分の面積は、全面積の１／３を超える。
<Anti-mold property>
Evaluation is performed in accordance with “mold resistance test method (wet method)” of JIS Z 2911: 2010. However, pretreatment with running water will not be implemented. Test period: 1 week, 2 weeks, 4 weeks.
Test bacteria: Group 1 Aspergillus niger, Group 2 Penicillium citrinum, Group 4 Cladosporium cladosporiides, Group 5 ketium globosum in JIS Z 2911.
(Evaluation criteria for mold resistance)
0: No hyphal growth is observed in the inoculated part of the sample or test piece.
1: The area of the growing part of the mycelium observed in the inoculated part of the sample or the test piece does not exceed 1/3 of the total area.
2: The area of the growth part of the mycelium recognized in the inoculated part of the sample or the test piece exceeds 1/3 of the total area.
実施例からも明らかなように、実施例１〜４は、高い透湿度と適切な吸湿率、高いガスバリア性をもつと同時に長期間安定した防カビ性を有しており、優れたエレメント用原紙であった。比較例１〜３は、安定した防カビ性は有しておらず、また比較例４で使用した防カビ剤は薬液中に分散しづらく沈降が確認され、エレメント用原紙に所定量が付着しなかったと考えられ、やはり安定した防カビ性は得られなかった。 As is clear from the examples, Examples 1 to 4 have high moisture permeability, appropriate moisture absorption, high gas barrier properties, and at the same time have stable anti-mold properties for a long period of time. Met. Comparative Examples 1 to 3 do not have a stable antifungal property, and the antifungal agent used in Comparative Example 4 is difficult to disperse in the chemical solution and confirmed to settle, and a predetermined amount adheres to the element base paper. It was thought that there was no antifungal property.
本発明の全熱交換器エレメント用原紙は、高い全熱交換効率と長期間にわたる高い防カビ性能を有するため、熱交換換気装置用途に極めて有用な基材である。 The base paper for a total heat exchanger element of the present invention has a high total heat exchange efficiency and a high antifungal performance over a long period of time, and is therefore a very useful substrate for heat exchange ventilator applications.
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Also Published As
| Publication number | Publication date |
|---|---|
| CN105274898A (en) | 2016-01-27 |
| JP6443246B2 (en) | 2018-12-26 |
| KR20160008981A (en) | 2016-01-25 |
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