JP2010013753A - Water-repellent, highly humidity-conditioning japanese paper sheet material and method for producing the same - Google Patents

Water-repellent, highly humidity-conditioning japanese paper sheet material and method for producing the same Download PDF

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JP2010013753A
JP2010013753A JP2008173418A JP2008173418A JP2010013753A JP 2010013753 A JP2010013753 A JP 2010013753A JP 2008173418 A JP2008173418 A JP 2008173418A JP 2008173418 A JP2008173418 A JP 2008173418A JP 2010013753 A JP2010013753 A JP 2010013753A
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fiber
paper layer
humidity
repellent
water
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Fumio Watanabe
文雄 渡辺
Yohei Ishiune
洋平 石畝
Katsuhiko Goto
勝彦 呉藤
Sasagu Terao
奉 寺尾
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Maruwa:Kk
株式会社丸和
Fukui Prefecture
福井県
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<P>PROBLEM TO BE SOLVED: To provide a water-repellent, highly humidity-conditioning Japanese paper sheet material having excellent humidity-conditioning functions over medium humidity and high humidity regions and even having a thin shape while having feeling and texture of Japanese paper, providing excellent designability and operability, and mild to the environment after disposal, and to provide a method for producing the sheet material. <P>SOLUTION: The water-repellent, highly humidity-conditioning Japanese paper sheet material is produced as follows. A natural fiber material of an auxiliary feedstock, having a diameter nearly equal to that of a hemp fiber material of a main feedstock and also having good entangling properties is mixed with the hemp fiber material, and a fiber material having an average fiber diameter and an average fiber length smaller than those of the hemp fiber material and the natural fiber material is added thereto as a space-regulating fiber material. The resultant mixture is subjected to papermaking to provide a base material paper layer 1. A humidity-conditioning paper layer 2 formed on the base material paper layer 1 in a layered state by papermaking, and obtained by adding a calcium silicate hydrate powder having a prescribed particle degree not permeating into the fiber space of the base material paper layer 1 to the hemp fiber material and the natural fiber material of the auxiliary feedstock contained in the base material paper layer 1, and a decorative paper layer 3 formed on the humidity-conditioning layer 2 in a layered state by papermaking, obtained by applying water-repellent processing onto the surface and having air permeability are laminated and integrated on the base material paper layer 1. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、主に内装に用いる調湿シート材の改良、詳しくは、室内空間の相対湿度を中湿度域(相対湿度50〜75%)から高湿度域(相対湿度75〜100%)に亘って自律的に調湿することを可能とし、かつ、薄くて丈夫で汚れ難く製造面でも非常に好都合な撥水性高調湿和紙シート材およびその製造方法に関するものである。   The present invention is an improvement of a humidity control sheet material mainly used for interiors. Specifically, the relative humidity of an indoor space ranges from a medium humidity range (relative humidity 50 to 75%) to a high humidity range (relative humidity 75 to 100%). The present invention relates to a water-repellent high-harmonic humidity Japanese paper sheet material that is capable of autonomously adjusting humidity and that is thin, strong, and resistant to dirt, and is very convenient in terms of manufacturing, and a method for manufacturing the same.
近年では、室内環境における不快な湿気や結露を防止するために中湿度域から高湿度域の調湿性を備えた内装用建材の利用が進んでおり、これらの調湿建材の主な共通課題として、いかに目的とする機能性無機粉体を効率よく基層に担持するかということがあり、その解決手段として有機エマルジョンや合成樹脂がバインダーとして用いられ、様々な組成や構造の調湿建材が提案されている。   In recent years, in order to prevent unpleasant moisture and dew condensation in the indoor environment, the use of interior building materials with humidity control in the middle to high humidity range has progressed, and the main common problem of these humidity control building materials is However, there is a question of how efficiently the desired functional inorganic powder is supported on the base layer. As a solution, organic emulsions and synthetic resins are used as binders, and humidity control building materials with various compositions and structures have been proposed. ing.
そして、かかる調湿材料における調湿性能の一般的基準としては、調湿建材の信頼性確保を目的として、社団法人日本建材産業・住宅設備協会によって「調湿建材登録・表示規定」が制定されている(非特許文献1)。   As a general standard for humidity conditioning performance in such humidity conditioning materials, the Japan Building Materials Industry and Housing Equipment Association established the “Regulation for Humidity Control Building Material Registration and Display” for the purpose of ensuring the reliability of humidity conditioning building materials. (Non-Patent Document 1).
この規定によると、相対湿度を50%から75%に変化させた際、12時間内に29g/m以上吸湿し、75%から50%の放湿過程では12時間内に吸湿量の70%の放湿量を有するものが調湿性能基準を満たすとされている。 According to this regulation, when the relative humidity is changed from 50% to 75%, it absorbs 29 g / m 2 or more within 12 hours, and in the process of releasing moisture from 75% to 50%, 70% of the moisture absorption within 12 hours. It is said that those having a moisture release amount satisfy the humidity control performance standard.
前記の試験方法は「JIS A 1470−1」において詳細に定められているが、通常は、ボード類のように厚みのある製品でないとその認定基準に合格することは困難であり、壁紙のように薄い材料で基準を満たすものは現存していない。   The above test method is defined in detail in “JIS A 1470-1”, but it is usually difficult to pass the certification standard unless it is a thick product such as boards, like wallpaper. No thin material that meets the standards currently exists.
従来、調湿和紙壁紙としては、パルプ繊維、不織布、フィルム等の可撓性を有する基材の表面に、無機多孔体が有機物エマルジョンをバインダーとして担持した吸放湿層が塗布形成された機能性壁紙や撥水調湿部材(特許文献1、2)が知られている。   Conventionally, as moisture-conditioned Japanese paper wallpaper, a moisture absorbing / releasing layer in which an inorganic porous material carries an organic emulsion as a binder is applied and formed on the surface of a flexible substrate such as pulp fiber, nonwoven fabric, film, etc. Wallpapers and water-repellent humidity control members (Patent Documents 1 and 2) are known.
しかしながら、それらの材料や方法は可撓性や製造コストの面では優れるものの、不織布や紙、プラスチックフィルム等からなる基材上に、調湿性などの機能を有する無機粉体を、有機エマルジョンで担持させた層に担わせているため、有機エマルジョンによる透湿性能の低下に加えて意匠の面でも制限されてしまい、和紙の質感を持つ軽薄なシート状壁材では、上記<非特許文献1>に記載されているような中湿度域における短時間での調湿性能基準を満足させることはできなかった。   However, although these materials and methods are excellent in terms of flexibility and manufacturing cost, inorganic powder having functions such as humidity control is supported on an organic emulsion on a substrate made of nonwoven fabric, paper, plastic film, etc. In addition to the decrease in moisture permeation performance due to the organic emulsion, it is limited in terms of design as well, and in the light and thin sheet-like wall material having the texture of Japanese paper, <Non-Patent Document 1> It was not possible to satisfy the humidity control performance standards in a short time in the medium humidity range as described in the above.
また、<特許文献2>では、有機エマルジョンを用いつつ透湿性を確保するために、撥水性の粉体を用いることで有機エマルジョンが乾燥硬化しても通気を確保する方法が記載されているが、この場合においても基材への担持が塗布乾燥硬化法であるので、面積あたりの調湿性能を高めて認定基準を満たそうとすれば厚みが増して単位面積あたりの重量が重くなるし、また、施工時の継ぎ目が目立ってしまい、更に、和紙の質感を付与することができないこと等の欠点があった他、リサイクルが困難で廃棄後の環境負荷面においても問題があった。   Further, <Patent Document 2> describes a method for ensuring air permeability even when the organic emulsion is dried and cured by using water-repellent powder in order to ensure moisture permeability while using the organic emulsion. Even in this case, since the support on the base material is a coating drying and curing method, increasing the humidity conditioning performance per area and satisfying the certification standard will increase the thickness and increase the weight per unit area, In addition, the seams at the time of construction are conspicuous, and there are also other disadvantages such as the inability to impart the texture of Japanese paper, and there are also problems in terms of environmental impact after disposal due to difficulty in recycling.
そしてまた、機能層として抄造法で形成するものとしては、炭、アパタイト、ゼオライト等の調湿性に優れる粒状添加剤を中間層とし、その両側に和紙を積層したサンドイッチ構造の和紙(特許文献3)や、人工ゼオライト粉体とパルプ等天然繊維素材で凝集フロック状に担持させた消臭調湿紙(特許文献4)等が知られている。   In addition, as a functional layer formed by a papermaking method, a sandwich paper in which a granular additive having excellent humidity control properties such as charcoal, apatite, zeolite, etc. is used as an intermediate layer, and Japanese paper is laminated on both sides thereof (Patent Document 3). Also known is deodorized moisture-controlled paper (Patent Document 4) that is supported in an aggregated floc form with natural fiber materials such as artificial zeolite powder and pulp.
しかしながら、<特許文献3>には、単にサンドイッチ構造が述べられているのみであり、通常の和紙製造法では、抄造する際に基層から粉体が流出したり、施工時の切断加工では端部の機能性粒子が脱落するという問題があり、粉体の調湿性能も低く、<非特許文献1>記載の基準を満足できなかった。   However, <Patent Document 3> only describes a sandwich structure, and in a normal Japanese paper manufacturing method, powder flows out of the base layer during papermaking, or in the cutting process during construction, an end portion is used. In other words, the functional particles of the powder fall off, the humidity control performance of the powder is low, and the criteria described in <Non-Patent Document 1> cannot be satisfied.
更にまた、<特許文献2、3>に見られるように調湿性能をゼオライトに依存した壁紙は、ゼオライトの吸湿特性は低湿度域での吸湿性は高いものの中湿度域や高湿度での吸湿や放湿能力は無いに等しいくらい僅かであるため、これもまた<非特許文献1>が求めるような性能確保はできない。   Furthermore, as can be seen in <Patent Documents 2 and 3>, the wallpaper that relies on zeolite for humidity control performance has high hygroscopicity in the low humidity range, but the hygroscopic property in the medium and high humidity ranges. In addition, since the moisture release capacity is as small as it is not, it is impossible to ensure the performance as required by <Non-Patent Document 1>.
そのほか、調湿建材としてはロックウールボードに活性炭、シリカゲル、ゼオライト、アロフェン等の吸放湿材料を配合し、抄造した後、フェノール樹脂を含浸させて一定の強度を持たせた調湿板材等も提案されている(特許文献5)。   In addition, as humidity control building materials, humidity control boards made of rock wool board with moisture absorption / release materials such as activated carbon, silica gel, zeolite, allophane, etc. It has been proposed (Patent Document 5).
しかしながら、<特許文献5>に見られるような板材や無機タイルでは、撓み性もなく切断作業や貼り付け作業等の施工性が悪いことや、単位面積当たりの重量が重いこと、また、工賃が紙材料を基本としたものよりも高価になるという問題があった。   However, plate materials and inorganic tiles such as those found in <Patent Document 5> are not flexible and have poor workability such as cutting work and pasting work, heavy weight per unit area, and labor costs. There was a problem that it was more expensive than those based on paper materials.
なお、シートの中間層や表層に不織布や合成繊維を使用する場合は、和紙のように抄造成形では無機粉体を担持しにくく、パルプ繊維との絡みやなじみも悪く、抄造法では製造が困難なこと、あるいは和紙調の多様な意匠性を付与しにくいことが問題であり、<非特許文献1>の認定基準の満足もまた困難であった。   In addition, when using non-woven fabric or synthetic fiber for the intermediate layer or surface layer of the sheet, it is difficult to carry inorganic powder in papermaking molding as in Japanese paper, and entanglement and familiarity with pulp fibers are poor, making it difficult to produce by papermaking method. In addition, it is difficult to impart various design properties of Japanese paper, and it is also difficult to satisfy the certification standard of <Non-Patent Document 1>.
更にまた、従来の和紙を内装壁材として使用する場合、防汚性が大きな課題としてあったことから、近年は撥水処理することが求められ、一部商品化もされているが、従来の撥水コーティング法では、調湿性を阻害するという問題があった。
社団法人日本建材産業・住宅設備産業協会発行 「調湿建材登録・表示制度」に関する調湿建材登録・表示規定 特開2004−300648 特開2005−105433 特開2004−52152 特開2004−277982 特開2003−20734
Furthermore, when conventional Japanese paper is used as an interior wall material, the antifouling property has been a major issue. In recent years, water repellent treatment has been required and some products have been commercialized. The water repellent coating method has a problem of inhibiting humidity control.
Humidity control building material registration and labeling regulations related to "Humidity control building material registration and labeling system" issued by Japan Building Materials Industry and Housing Equipment Industry Association JP-A-2004-300648 JP 2005-105433 A JP 2004-52152 A Japanese Patent Application Laid-Open No. 2004-277782 JP2003-20734
本発明は、上記の如き問題に鑑みて為されたものであり、その目的とするところは、和紙の風合いや質感を有しつつ、薄い形状であっても中湿度域および高湿度域に亙って優れた調湿機能を備え、かつ、意匠性や施工性にも優れ、しかも、廃棄後も環境に優しい撥水性高調湿和紙シート材およびその製造方法を提供することにある。   The present invention has been made in view of the problems as described above, and the object of the present invention is to maintain the texture and texture of Japanese paper, and even in the thin and high humidity range, even in the thin shape. Another object of the present invention is to provide a water repellent and high-humidity Japanese paper sheet material that has an excellent humidity control function, is excellent in design and workability, and is environmentally friendly after disposal, and a method for producing the same.
本発明者が上記課題を解決するために採用した手段を添付図面を参照して説明すれば次のとおりである。   Means employed by the present inventor for solving the above-described problems will be described with reference to the accompanying drawings.
即ち、本発明は、主原料である麻繊維材に、これと略同径であって、かつ、絡み性が良好な副原料の天然繊維材を混合し、さらにこれら麻繊維材および天然繊維材よりも平均繊維径および平均繊維長の小なる繊維材を間隙調整繊維材として添加して抄造された基材紙層1と;
この基材紙層1上に層着状態に抄造され、かつ、基材紙層1に含まれる麻繊維材と副原料の天然繊維材に、前記基材紙層1の繊維間隙に不透過な所定粒度の珪酸カルシウム水和物(以下、「C−S−H」と略記する)粉体を混入した調湿紙層2と;
この調湿紙層2上に層着状態に抄造されて形成され、かつ、表面に撥水加工が施された通気性を有する化粧紙層3とを積層して一体に構成した点に特徴がある。
That is, the present invention mixes a hemp fiber material, which is a main raw material, with a natural fiber material of an auxiliary material that has substantially the same diameter and good entanglement, and further, these hemp fiber material and natural fiber material A base paper layer 1 made by adding a fiber material having a smaller average fiber diameter and average fiber length as a gap adjusting fiber material;
The base paper layer 1 is made into a layered state, and the hemp fiber material and auxiliary natural fiber material contained in the base paper layer 1 are impermeable to the fiber gaps of the base paper layer 1. A humidity control paper layer 2 mixed with calcium silicate hydrate (hereinafter abbreviated as “C—S—H”) powder of a predetermined particle size;
It is characterized in that it is integrally formed by laminating a breathable decorative paper layer 3 formed on the humidity-controlling paper layer 2 in a layered state and having a water repellent finish on the surface. is there.
また、本発明は、上記課題を解決するために、必要に応じて上記手段に加え、基材紙層1の麻繊維材を、乾燥重量割合で麻繊維材を少なくとも50%以上含むようにするという技術的手段を採用することができる。   Moreover, in order to solve the said subject, in addition to the said means, this invention makes the hemp fiber material of the base paper layer 1 contain hemp fiber material at least 50% or more by dry weight ratio as needed. Technical means can be adopted.
また、本発明は、上記課題を解決するために、必要に応じて上記手段に加え、調湿紙層2を、C−S−H粉体を乾燥重量割合が25〜70%で、麻繊維材と針葉樹パルプ繊維と広葉樹パルプ繊維からなる天然パルプ繊維を少なくとも乾燥重量割合で30%以上含み、それらを天然高分子バインダーによって結合形成するという技術的手段を採用することができる。   Moreover, in order to solve the said subject, this invention adds the said means as needed, the humidity-control paper layer 2, C-S-H powder is dry weight ratio 25-70%, hemp fiber It is possible to employ a technical means of including at least 30% or more of a natural pulp fiber composed of wood, softwood pulp fiber and hardwood pulp fiber in a dry weight ratio and bonding them with a natural polymer binder.
また、本発明は、上記課題を解決するために、必要に応じて上記手段に加え、基礎紙層1と調湿紙層2の上部の意匠層である化粧紙層3を、乾燥重量割合で麻繊維材80〜90%と針葉樹パルプを主原料とする繊維が10〜20%の乾燥重量割合で混合・抄造するという技術的手段を採用することができる。   Moreover, in order to solve the said subject, in addition to the said means as needed, this invention is the decorative paper layer 3 which is the design layer of the upper part of the basic paper layer 1 and the humidity-control paper layer 2 in a dry weight ratio. It is possible to employ a technical means that 80 to 90% of hemp fiber material and fibers mainly composed of softwood pulp are mixed and made at a dry weight ratio of 10 to 20%.
また、本発明は、上記課題を解決するために、必要に応じて上記手段に加え、化粧紙層3の表面凹凸の微細頭頂部において、点状に撥水剤が付着加工するという技術的手段を採用することができる。   Further, in order to solve the above-described problems, the present invention provides a technical means in which a water repellent is attached and processed in a dot-like manner on the fine top of the surface irregularities of the decorative paper layer 3 in addition to the above means as necessary. Can be adopted.
また、本発明は、上記課題を解決するために、必要に応じて上記手段に加え、調湿紙層2のC−S−H粉体を、粒径1μm以上で、かつ、加熱脱水処理されたものにするという技術的手段を採用することができる。   In addition, in order to solve the above-mentioned problems, the present invention, in addition to the above-described means, the C—S—H powder of the humidity control paper layer 2 has a particle diameter of 1 μm or more and is subjected to heat dehydration treatment. Technical means can be adopted.
また、本発明は、上記課題を解決するために、必要に応じて上記手段に加え、基材紙層1および調湿紙層2の主原料における麻繊維材をマニラ麻繊維にするという技術的手段を採用することができる。   Further, in order to solve the above-mentioned problems, the present invention provides technical means for making the hemp fiber material in the main raw material of the base paper layer 1 and the humidity control paper layer 2 into manila hemp fibers in addition to the above means as necessary. Can be adopted.
また、本発明は、上記課題を解決するために、必要に応じて上記手段に加え、基材紙層1および調湿紙層2における副原料の天然繊維材を針葉樹パルプ繊維にするという技術的手段を採用することができる。   In addition, in order to solve the above-described problems, the present invention provides a technical technique in which a natural fiber material as a secondary raw material in the base paper layer 1 and the humidity control paper layer 2 is conifer pulp fiber in addition to the above-described means as necessary. Means can be employed.
また、本発明は、上記課題を解決するために、必要に応じて上記手段に加え、基材紙層1における間隙調整繊維材を広葉樹パルプ繊維にするという技術的手段を採用することができる。   Moreover, in order to solve the said subject, in addition to the said means as needed, this invention can employ | adopt the technical means of making the clearance adjustment fiber material in the base paper layer 1 into hardwood pulp fiber.
また、本発明は、上記課題を解決するために、必要に応じて上記手段に加え、基材紙層1および調湿紙層2、化粧紙層3に、それぞれ天然高分子から成る植物性バインダー材料を混合するという技術的手段を採用することができる。   In order to solve the above problems, the present invention provides a vegetable binder comprising a natural polymer in each of the base paper layer 1, the humidity control paper layer 2 and the decorative paper layer 3 in addition to the above means as necessary. Technical means of mixing the materials can be employed.
また、本発明は、上記課題を解決するために、必要に応じて上記手段に加え、化粧紙層3の主原料を麻繊維材にするという技術的手段を採用することができる。   Moreover, in order to solve the said subject, in addition to the said means as needed, this invention can employ | adopt the technical means of making the main raw material of the decorative paper layer 3 into a hemp fiber material.
また、本発明は、上記課題を解決するために、必要に応じて上記手段に加え、麻繊維材を主原料とし、これと略同径であって、かつ、絡み性の良好な天然繊維材を副原料として、植物性バインダーとともに水中に遊離状に分散混合させ、更に前記麻繊維材および天然繊維材よりも平均繊維径および平均繊維長の小なる繊維材を間隙調整繊維材として添加して基材紙料液を調製し、この基材紙料液から前記各繊維を含む基材紙層を抄き取った後、この抄き取った前記基材紙層が乾燥する前に、主原料の麻繊維材および副原料の天然繊維材とを含む紙料液に前記基材紙層の繊維間隙に不透過な所定粒度のC−S−H粉体を混入して調製した調湿紙料液を抄き取って調湿紙層を層着せしめ、ついで、これら基材紙層および調湿紙層が乾燥する前に、この調湿紙層の上に、紙繊維材料からなる紙料液から紙繊維を抄き取って化粧紙層を層着形成して乾燥処理し、然る後、前記化粧紙層の表面に撥水加工を施すという技術的手段を採用することができる。   Further, in order to solve the above-mentioned problems, the present invention uses a hemp fiber material as a main raw material in addition to the above means as necessary, and is a natural fiber material having substantially the same diameter as this and having good entanglement. As a secondary raw material, dispersed in water together with a vegetable binder, and further added as a gap adjusting fiber material a fiber material having an average fiber diameter and an average fiber length smaller than those of the hemp fiber material and natural fiber material. After preparing a base stock liquid and making a base paper layer containing each of the fibers from the base stock liquid, the main raw material is dried before the base paper layer is dried. Humidity control paper stock prepared by mixing a CSH powder having a predetermined particle size that is impermeable to the fiber gaps of the base paper layer into a stock solution containing hemp fiber material and natural fiber material of auxiliary material The liquid is drawn out to form a humidity control paper layer, and then, before the base paper layer and the humidity control paper layer are dried, On the moisture-controlling paper layer, paper fibers are drawn from a paper solution made of a paper fiber material, and a decorative paper layer is formed and dried. After that, the surface of the decorative paper layer is repelled. A technical means of applying water processing can be employed.
本発明においては、植物繊維の中でも中湿度域における優れた調湿性と高い強度とを兼ね備え、かつ、麻繊維材を主原料として基材紙層を抄造するとともに、基材紙層上には、基材紙層と同じく繊維が太めで粉体を担持するための適度な隙間が多く形成され易い麻繊維材を主原料とし、更にこれらの原料繊維に高湿度域での調湿性能が珪藻土に比べて約3倍高いC−S−H粉体を混入して調湿紙層を形成したことにより、中湿度域から高湿度域にわたって自律した高い調湿性能を示す和紙シート材を作製することが可能となり、しかも、珪藻土を用いて同レベルの調湿性能を実現した場合に比べてシート材の薄型化及び軽量化を図ることもできる。   In the present invention, it combines excellent humidity control and high strength in the middle humidity region among plant fibers, and papermaking a base paper layer using hemp fiber material as a main raw material, on the base paper layer, As with the base paper layer, hemp fiber material that is thick and easy to form a lot of gaps for supporting powder is used as the main raw material, and humidity control performance in high humidity range is also achieved in diatomaceous earth. Producing a Japanese paper sheet material that exhibits high humidity control performance autonomously from a medium humidity range to a high humidity range by mixing a C-S-H powder that is about three times higher than that of the humidity control paper layer. In addition, the sheet material can be made thinner and lighter than when the humidity control performance of the same level is realized using diatomaceous earth.
また、基材紙層には、主原料の麻繊維材および副原料の天然繊維材に加えて、繊維径及び繊維長が小さい間隙調整用の繊維材を添加して繊維同士の隙間のサイズを小さくしたことにより、調湿紙層の抄造時において、微小なC−S−H粉体が基材紙層の繊維に引っかかり易くなってフィルター効果を奏するため、粉体の漏れ落ちが抑制され歩留りが改善されて製造コストを低減化できる。   In addition to the hemp fiber material of the main raw material and the natural fiber material of the auxiliary raw material, a fiber material for gap adjustment having a small fiber diameter and fiber length is added to the base paper layer to reduce the size of the gap between the fibers. By making it smaller, the fine C—S—H powder is easily caught by the fibers of the base paper layer when producing the humidity control paper layer, and a filter effect is produced. Can be improved and the manufacturing cost can be reduced.
また、本発明では、調湿紙層上に更に化粧紙層を形成することで意匠性を高めるとともに、この化粧紙層を介在させることによって調湿紙層のC−S−H粉体の外への飛び出しを防止でき、しかも、防汚効果を付与する撥水加工を化粧紙層の表面に行うことで、C−S−H粉体に直接撥水剤が付着する問題も解消される。   In the present invention, the decorative paper layer is further formed on the humidity control paper layer to improve the design, and by interposing this decorative paper layer, the C—S—H powder of the humidity control paper layer is removed. When the surface of the decorative paper layer is subjected to a water-repellent treatment that imparts an antifouling effect, the problem that the water-repellent agent directly adheres to the CSH powder is also solved.
更に、本発明によれば、抄造段階で基材紙層は十分な強度を備えているため、調湿紙層となるスラリー中の粉体を歩留まりよく残留せしめ、調湿紙層は麻繊維材や針葉樹パルプ繊維などの天然パルプ繊維が中湿度域での調湿機能の発現と高湿度域を高めるための調湿粉体であるC−S−Hを強固に大量に担持することができる。   Furthermore, according to the present invention, since the base paper layer has sufficient strength at the paper making stage, the powder in the slurry that becomes the humidity control paper layer is left with a high yield, and the humidity control paper layer is a hemp fiber material. And natural pulp fibers, such as softwood pulp fibers, can firmly and massively support C—S—H, which is a humidity-controlling powder for improving the humidity-control function in the middle-humidity region and increasing the high-humidity region.
また、化粧紙層の表層は和紙の風合いを持つ多様な意匠が可能となり、化粧紙層の最表面に施した撥水処理によって、軽薄で調湿建材認定基準に合致した撥水性高調湿和紙シート材が得られるので、これを内装壁材として用いることで自立的調湿機能を発現し、室内空気の快適湿度環境を提供することが可能となる。   In addition, the surface layer of the decorative paper layer enables a variety of designs with the texture of Japanese paper, and the water-repellent high-humidity humidified Japanese paper sheet conforms to the moisture-conditioning building material certification standards by the water-repellent treatment applied to the outermost surface of the decorative paper layer. Since a material is obtained, it is possible to provide a comfortable humidity environment for indoor air by using this as an interior wall material to develop a self-sustaining humidity control function.
また、従来の内装用調湿壁材は、ボードやタイル状のものがほとんどであり、厚みがある分、継ぎ目が目立つという欠点があり、また、類似のシート状製品も同様の欠点があるが、本願発明の撥水調湿和紙シートは、化粧紙層が和紙の繊維材からなっているので、継ぎ目となる箇所を施工後に一様に均すことによって表層の繊維が重なり合って目立たなくすることができる。   In addition, most of the conventional humidity control wall materials for interior use are boards and tiles, and there is a drawback that the seam is conspicuous because of the thickness, and similar sheet-like products have the same disadvantage. In the water-repellent moisture-controlled Japanese paper sheet of the present invention, since the decorative paper layer is made of Japanese paper fiber material, the surface layer fibers overlap each other by making the joints uniform even after construction, so that the surface layers overlap. Can do.
さらに、本発明品は、繊維材やバインダーが天然原料主体であり、調湿粉体として使用する加熱脱水C−S−Hは化学成分が珪酸とカルシウムであるので、廃棄後も肥料や土壌改良材などとして利用することができるので、極めて環境に優しいという特徴がある。   Furthermore, the product of the present invention is mainly composed of natural raw materials such as fiber material and binder, and the heat-dehydrated CSH used as the humidity control powder is composed of silicic acid and calcium. Since it can be used as a material, it is extremely environmentally friendly.
また、本願発明は、従来技術にあるような粒子の粒径や繊維の長さのみを制御する方法ではなく、基材となる繊維を幅が太くて強度の強いマニラ麻を主原料とし、同様な繊維幅である針葉樹パルプやそれよりも繊維幅の細い広葉樹パルプ等を併せて用いることによって、抄造性と繊維の絡みがもたらす間隙の量と大きさを最適化し、調湿紙層を形成させるための粒子の透過防止フィルターとしての機能を付与することができ、かつ、製品強度の規定を満足せしめることもできる。   In addition, the present invention is not a method for controlling only the particle diameter and fiber length as in the prior art, but the fiber as a base material is made of high-strength Manila hemp as a main raw material. In order to optimize the amount and size of papermaking and the amount of gap caused by fiber entanglement by using conifer pulp with fiber width and broad-leaved wood pulp with narrower fiber width, etc., to form a humidity control paper layer The function of the particles as a permeation prevention filter can be imparted, and the product strength can be satisfied.
したがって、調湿建材としての調湿機能に優れるだけでなく、使用面や大量生産を前提とする製造面でも非常に有利な高調湿シート材を提供でき、更に、要に臨んで本シート材をタンスの中や下駄箱内に入れて吸湿や消臭するなどの広範囲に亙り使用することもできることから、本発明の実用的利用価値は頗る高い。   Therefore, it is possible to provide a high-humidity humidity sheet material that is not only superior in humidity control function as a humidity control building material, but also very advantageous in terms of use and manufacturing, premised on mass production. The practical use value of the present invention is very high because it can be used over a wide range of moisture absorption and deodorization by placing it in a chest or in a clog box.
本発明を実施するための最良の形態を具体的に図示した図面に基づいて更に詳細に説明すると、次のとおりである。   BEST MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the present invention will be described in more detail with reference to the drawings specifically shown as follows.
本発明の実施形態は、図1および図2に示される。図1中において、符号1で指示するものは基材紙層であり、符号2で指示するものは調湿紙層である。そして、符号3で指示するものは、化粧紙層である。   An embodiment of the present invention is shown in FIGS. In FIG. 1, what is indicated by reference numeral 1 is a base paper layer, and what is indicated by reference numeral 2 is a humidity control paper layer. What is indicated by reference numeral 3 is a decorative paper layer.
まず、基材紙層1について説明する。この基材紙層1は、主原料の麻繊維材に、この麻繊維材と略同径であって、かつ、この麻繊維材との良好な絡み性を有する副原料の天然繊維材を混合し、更にこれらの麻繊維材や天然繊維材よりも平均繊維径および平均繊維長が小さい繊維材を間隙調整繊維材として添加した材料から形成されている。なお、主原料とは、混合材料の全重量に対して最大の重量部(特に50%以上)を占める原料をいう。   First, the base paper layer 1 will be described. This base paper layer 1 is mixed with the main raw material hemp fiber material, the auxiliary raw material natural fiber material having substantially the same diameter as the hemp fiber material and having good entanglement with the hemp fiber material. Further, the fiber is formed from a material obtained by adding a fiber material having an average fiber diameter and an average fiber length smaller than those of the hemp fiber material and natural fiber material as a gap adjusting fiber material. The main raw material refers to a raw material occupying the largest part by weight (particularly 50% or more) with respect to the total weight of the mixed material.
この基材紙層1(および後述する調湿紙層2)に用いる麻繊維材には、中湿度域での調湿機能に加えて強度が高く、繊維の絡みが良好で繊維間の細孔調整が可能であり、また後述する調湿紙層2の抄造行程(スラリー中)におけるC−S−Hの粉体を流失させないようにするために、繊維径が15〜40μmと天然繊維の中でも太くて丈夫なマニラ麻繊維を使用するとともに、、副原料の天然繊維材には、麻繊維材と同様に中湿度域の調湿機能を有して、かつ、繊維幅もマニラ麻繊維と略同じ10〜30μmであって、麻繊維材と非常に絡み易い針葉樹パルプ繊維を使用している。   The hemp fiber material used for the base paper layer 1 (and the humidity control paper layer 2 to be described later) has high strength in addition to the humidity control function in the middle humidity range, good fiber entanglement, and fine pores between the fibers. In order to prevent the C—S—H powder from being washed away in the paper making process (in the slurry) of the humidity-controlling paper layer 2 to be described later, the fiber diameter is 15 to 40 μm among natural fibers. Using thick and durable Manila hemp fiber, the natural fiber material of the auxiliary material has a humidity control function in the middle humidity range like hemp fiber material, and the fiber width is substantially the same as that of Manila hemp fiber. It is ˜30 μm, and softwood pulp fibers that are very easily entangled with the hemp fiber material are used.
なお、主原料の麻繊維材としては、マニラ麻以外のサイザル麻やケナフ、ジュートなどを使用することもでき、また、副原料の天然繊維材としては、調湿性を有しているものが望ましいが、基本的に麻繊維材に絡み易くて麻繊維材と同程度の長さと太さを持っているものならば、針葉樹パルプ繊維以外のものを使用することが可能である。   In addition, sisal hemp, kenaf, jute, etc. other than manila hemp can be used as the main raw material hemp fiber material. Basically, other than softwood pulp fibers can be used as long as they are easily entangled with the hemp fiber material and have the same length and thickness as the hemp fiber material.
本実施形態では、副原料の針葉樹パルプ繊維は、主原料のマニラ麻繊維に対して約9:1の割合(wt%)で配合している。   In this embodiment, the softwood pulp fiber of a subsidiary material is mix | blended in the ratio (wt%) of about 9: 1 with respect to the Manila hemp fiber of a main raw material.
また、基材紙層1に添加する間隙調整繊維材には、前記麻繊維材や針葉樹パルプ繊維に比べて中湿度域の調湿性能が高く、繊維径が5〜15μm程度と非常に細い広葉樹パルプ繊維を使用することが望ましい。   Further, the gap adjusting fiber material added to the base paper layer 1 has a high humidity control performance in the middle humidity range compared to the hemp fiber material and softwood pulp fiber, and a very thin hardwood having a fiber diameter of about 5 to 15 μm. It is desirable to use pulp fibers.
この間隙調整繊維材(特に広葉樹パルプ繊維)は、天然パルプの中でも最も繊維幅が細いうえ、叩解によって繊維に多くの分岐が発生することから繊維間の隙間も狭くまた粒子を捕捉するフィルター効果もいっそう高くすることができるが、多量に使用すると抄造段階での脱水(水抜け)も不良となるので、10wt%程度までに抑えることが望ましい。   This gap-adjusting fiber material (especially hardwood pulp fiber) has the narrowest fiber width among natural pulp, and many branches occur in the fiber by beating, so the gap between the fibers is narrow and the filter effect to trap particles Although it can be further increased, if it is used in a large amount, dehydration (drainage) at the paper making stage becomes poor, so it is desirable to suppress it to about 10 wt%.
また、この間隙調整繊維材についても調湿機能を有していることが好ましいが、麻繊維材や天然繊維材よりも平均繊維径および平均繊維長の小なる(細く短い)繊維材ならば広葉樹パルプ繊維以外からでも適宜選択することができ、繊維径および繊維長の設定が容易な化合繊維を採用することもできる。   In addition, it is preferable that the gap adjusting fiber material has a humidity control function. However, if the fiber material has an average fiber diameter and an average fiber length smaller (thin and shorter) than hemp fiber material or natural fiber material, it is a hardwood. It is possible to select appropriately from other than pulp fibers, and it is also possible to employ a compound fiber in which the fiber diameter and fiber length can be easily set.
次に、調湿紙層2について説明する。この調湿紙層2は、上記基材紙層1上に設けられる層であって、繊維間に適度な隙間が形成される繊維の太さおよび長さの麻繊維材(本実施形態では、「マニラ麻繊維」)を主原料とし、この麻繊維材に絡み性を有する針葉樹パルプ繊維を副原料として混合して、更にこれらに粒度が1〜100μmのC−S−H粉体を加えて形成したものである。   Next, the humidity control paper layer 2 will be described. The moisture conditioning paper layer 2 is a layer provided on the base paper layer 1 and is a hemp fiber material having a thickness and length of fibers (in this embodiment, an appropriate gap is formed between the fibers. "Manila hemp fiber") is used as a main raw material, and softwood pulp fiber with entanglement is mixed as an auxiliary raw material, and further C-S-H powder having a particle size of 1 to 100 μm is added thereto. It is a thing.
このC−S−H粉体としては、粉体と繊維との絡みが良好で極めて高性能な調湿粉体が効果的であることから、加熱脱水処理されたC−S−Hを用いる。なお、詳しくは、参考文献「J.Ceram.Soc.JAPAN 113[11]736−742(2005)」に記載されている。   As this C—S—H powder, heat-dehydrated C—S—H is used because a highly-conditioned humidity control powder with good entanglement between the powder and fibers is effective. Details are described in the reference document “J. Ceram. Soc. JAPAN 113 [11] 736-742 (2005)”.
また、この加熱脱水処理されたC−S−Hは、従来の珪酸カルシウム系建材の構成物質や、一般的に使用されている無機粉体である珪藻土等の3倍以上の極めて高い調湿性能を有する物質である。   In addition, this heat-dehydrated C—S—H is extremely high humidity control performance that is more than three times that of conventional calcium silicate building materials and diatomaceous earth, which is a commonly used inorganic powder. It is a substance having
さらにこの物質は、粉砕物の形状が針状粒子の集合体となっていることから、抄造時に繊維と絡みやすい性質がある他、低廉に大量に製造可能であり、廃棄後も土壌改良材としての認定基準も満足しているなど、環境負荷の面からも問題がない。   In addition, this material is a collection of acicular particles in the shape of the pulverized material, so it has the property of being easily entangled with fibers during papermaking and can be manufactured in large quantities at low cost. There is no problem from the aspect of environmental load, such as satisfying the certification standards.
なお、通常は結晶層間にナノレベルの間隙を持つ物質である110℃〜700℃の範囲で加熱脱水処理されたC−S−Hを用いるが、高い調湿機能を求める場合は高温域で加熱脱水処理されたC−S−Hを使用する方が好適であり、また、高い白色度を求める場合は不純物として含まれる鉄化合物の少ない原料で合成されたC−S−Hを用いるか、含まれている鉄化合物が酸化しない低温域で加熱脱水処理されたC−S−Hを使用することが望ましい。   Normally, C—S—H, which is a substance having a nano-level gap between crystal layers and heated and dehydrated in a range of 110 ° C. to 700 ° C., is used. It is preferable to use dehydrated C—S—H. When high whiteness is required, C—S—H synthesized from a raw material with a small amount of iron compounds contained as impurities is used or included. It is desirable to use C—S—H that has been heat-dehydrated in a low temperature range where the iron compound is not oxidized.
この調湿紙層2において、中湿度域における短時間での高い調湿性能を確保するためには、マニラ麻繊維と針葉樹パルプ繊維とから成る混合繊維材料を内割で20wt%以上配合する必要がある。   In order to ensure high humidity control performance in a short period of time in the medium humidity region in the humidity control paper layer 2, it is necessary to mix a mixed fiber material composed of Manila hemp fibers and softwood pulp fibers at an internal rate of 20 wt% or more. is there.
また、C−S−H粉体と前記混合繊維材料との配合割合は、中湿度域と高湿度域との調湿機能のバランスを考慮して決定することが望ましい。なお、C−S−H粉体を25%以上含有させた場合には、調湿紙層2に難燃性を付与することもできる。   Moreover, it is desirable to determine the blending ratio between the C—S—H powder and the mixed fiber material in consideration of the balance of the humidity control function between the medium humidity region and the high humidity region. Note that when the C—S—H powder is contained in an amount of 25% or more, the humidity-controlling paper layer 2 can be provided with flame retardancy.
最後に、化粧紙層3について説明する。この化粧紙層3は、上記調湿紙層2上に設けられる層であって、麻繊維材と針葉樹パルプ繊維を材料とし、表面には撥水加工が施され、かつ、通気性を有している。   Finally, the decorative paper layer 3 will be described. The decorative paper layer 3 is a layer provided on the humidity-controlling paper layer 2 and is made of hemp fiber material and softwood pulp fiber. The surface is water repellent and has air permeability. ing.
また、通気性を確保しつつ和紙の風合いを持ちながら多様な意匠を可能とするために、麻繊維材やコウゾ、ミツマタなどの比較的繊維長の長い和紙用天然繊維を主原料として用いることで意匠性と機能性を確保することができる。   In addition, in order to enable various designs while maintaining the breathability while maintaining the breathability of Japanese paper, natural fibers for Japanese paper with relatively long fiber lengths such as hemp fiber material, Kozo, and Mitsumata are used as the main raw material. Designability and functionality can be secured.
なお、化粧紙層3には意匠性や機能性の観点から、天然パルプ繊維を主原料としつつ人造繊維や他の機能性粉体や着色用材等を混入することもできる。混入する繊維材料は、例えば、和紙の風合いや機能性の確保や、各層を強く一体化せしめる点に加えて、和紙としての強度を上げるとともに、前記調湿紙層への湿気の流通を良くして透気度を高めるためにも、天然繊維材料でも繊維が太くて長いマニラ麻繊維材やコウゾ等を主原料として、針葉樹パルプを内割で10〜20重量部配合することが望ましい。この際、他にレーヨン、着色繊維、着色顔料等を配合することもできるし、表面にエンボス加工などを施して意匠性を付与することもできる。   In addition, from the viewpoint of design and functionality, the decorative paper layer 3 can be mixed with artificial fibers, other functional powders, coloring materials, and the like while using natural pulp fibers as a main raw material. The mixed fiber material, for example, ensures the texture and functionality of the Japanese paper, strongly integrates the layers, increases the strength of the Japanese paper, and improves the flow of moisture to the humidity control paper layer. In order to increase the air permeability, it is desirable that 10 to 20 parts by weight of softwood pulp is blended with a natural fiber material having thick and long Manila hemp fiber material or mulberry as a main raw material. At this time, rayon, colored fibers, colored pigments, and the like can also be blended, and the surface can be embossed to impart design properties.
そしてまた、化粧紙層3の撥水加工に用いる撥水剤は、安全性と価格、環境負荷等の観点からシリコーン系の水系撥水剤を用いるのが好ましいが、非水系でも良く、油煙などからの防汚が必要な場合はフッ素系の撥水剤を使用してもよい。   In addition, the water repellent used for the water repellent finish of the decorative paper layer 3 is preferably a silicone water repellent from the viewpoint of safety, price, environmental load, etc., but may be non-aqueous, such as oily smoke. Fluorine-based water repellent may be used when anti-staining is required.
以上のように構成される、機能及び役割の異なる基材紙層1及び調湿紙層2、化粧紙層3を順々に積層(本実施形態での各層の厚みの割合は、約1:3:1)して一体化することにより、中湿度域から高湿度域にわたって高い調湿機能を有し、かつ、薄くて丈夫な意匠性の高いシート材が形成される。   The base paper layer 1, the humidity control paper layer 2, and the decorative paper layer 3 having different functions and roles, which are configured as described above, are sequentially laminated (the ratio of the thickness of each layer in this embodiment is about 1: 3: 1) and integration makes it possible to form a sheet material having a high humidity control function from a middle humidity range to a high humidity range, and being thin and durable with high design properties.
『シート材の製造方法』
本実施形態のシート材の製造方法について以下に詳しく説明する。まず、麻繊維材を主原料とし、この麻繊維材と略同径であって、かつ、この麻繊維材との絡み性の良好な天然繊維材を副原料として、バインダーとともに水中に遊離状に分散混合させる。
"Production method of sheet material"
The manufacturing method of the sheet material of this embodiment will be described in detail below. First, hemp fiber material is used as the main raw material, and natural fiber material that is approximately the same diameter as this hemp fiber material and has good entanglement with this hemp fiber material is used as a secondary raw material and is freely released in water together with the binder. Disperse and mix.
このバインダーとして吸放湿性を阻害しない天然高分子バインダーを用いる一方、混合・混練・水分調整し、得られたスラリー液を基層上に流して抄造脱水する。その後の工程によってC−S−H粒子は繊維同士の間隙に潜り込んで潰れ、両繊維材といっそう強く絡み合うことで有機エマルジョンを使わなくても強固に担持一体化せしめることができる。   A natural polymer binder that does not inhibit moisture absorption / release properties is used as the binder, while mixing, kneading, and moisture adjustment are performed, and the resulting slurry is poured onto the base layer for paper dehydration. In the subsequent process, the C—S—H particles sink into the gaps between the fibers and are crushed and entangled more strongly with both fiber materials, so that they can be firmly supported and integrated without using an organic emulsion.
この際、トロロアオイ等の天然高分子から成る植物性バインダーを採用すれば、シート材の調湿性能が更に向上するだけでなく、生分解性を有しているため各紙層の繊維材に植物繊維のみを使用すれば環境に非常に優しいシート材にすることができる。   At this time, if a vegetable binder made of a natural polymer such as troro-aoi is used, not only the humidity control performance of the sheet material is further improved, but also the plant fiber is added to the fiber material of each paper layer because it has biodegradability. If only is used, the sheet material can be made very environmentally friendly.
そして、上記麻繊維材および天然繊維材よりも平均繊維長の小なる繊維材を間隙調整繊維材として添加して基材紙料液を調製し、この基材紙料液から前記各繊維を含む基材紙層1を抄き取る。   Then, a base material liquid is prepared by adding a fiber material having an average fiber length smaller than that of the hemp fiber material and natural fiber material as a gap adjusting fiber material, and each of the fibers is included from the base material liquid. The base paper layer 1 is removed.
なお、抄造時の脱水性は、細く細かい広葉樹パルプ繊維の配合量を増減して繊維間隙の大きさを変更することによって、適宜調整することができる。   In addition, the dewaterability at the time of papermaking can be suitably adjusted by changing the magnitude | size of a fiber gap | interval by increasing / decreasing the compounding quantity of fine fine hardwood pulp fiber.
この間隙調整繊維材として使用される広葉樹パルプ繊維は、天然パルプ繊維の中でも最も繊維幅が細いうえ、叩解によって繊維に多くの分岐が発生することから粒子を捕捉するフィルター効果も高いが、多量に使用すると抄造段階での基材紙層1の水抜けも不良となるので、配合割合は10wt%程度に抑えることが望ましく、叩解処理条件なども実験的に決定することが好ましい。   The hardwood pulp fiber used as the gap adjusting fiber material has the narrowest fiber width among the natural pulp fibers, and the fiber has many branches due to beating. If used, the water loss of the base paper layer 1 at the paper making stage will be poor, so the blending ratio is desirably suppressed to about 10 wt%, and the beating treatment conditions are preferably determined experimentally.
そして、抄き取った基材紙層1が乾燥する前に、主原料の麻繊維材と副原料の天然繊維材とを含む紙料液に粒度が1μm〜5mmのC−S−H粉体を混入して調製した調湿紙料液を抄き取って調湿紙層2を層着せしめる。この際、澱粉を調湿紙層2に添加することにより、C−S−H粉体と各繊維材との絡み性をより強化して、シートを施工する際における切断加工時の粉体の脱落を防止することができる。   Then, before the paper base paper layer 1 is dried, the C—S—H powder having a particle size of 1 μm to 5 mm is added to the paper stock liquid containing the main raw material hemp fiber material and the auxiliary raw material natural fiber material. The humidity-controlling paper stock solution prepared by mixing the paper is made and the humidity-controlling paper layer 2 is deposited. At this time, by adding starch to the humidity control paper layer 2, the entanglement between the CSH powder and each fiber material is further strengthened, and the powder at the time of cutting when the sheet is applied is reduced. Dropout can be prevented.
調湿紙層2を抄造する際は、中湿度域における短時間内での高い調湿性発現のために、天然繊維としてマニラ麻と針葉樹パルプを主原料とする繊維材料を、調湿粉体に対して内割で20〜60%の重量割合で配合し、かつ、バインダーは吸放湿性能を阻害しない澱粉やトロロアオイ等の天然高分子バインダーを使用して抄造法で吸放湿層を形成することが望ましい。   When making the humidity control paper layer 2, in order to achieve high humidity control within a short period of time in the middle humidity range, fiber materials made mainly of manila hemp and softwood pulp as natural fibers are used for the humidity control powder. A moisture absorption / release layer is formed by a papermaking method using a natural polymer binder such as starch or troro-aoi that does not impair the moisture absorption / release performance. Is desirable.
この際、C−S−Hの粉体と繊維との配合量割合は、調湿機能が認定基準を上回ることに加えて、難燃性の認定基準をも満足できる範囲にすることが望ましいが、機能性向上のために、適宜、その他の難燃剤を併せて用いることもできる。   At this time, it is desirable that the blending ratio of the C—S—H powder and the fiber is within a range in which the humidity control function exceeds the certification standard and also the flame retardant certification standard can be satisfied. In order to improve functionality, other flame retardants can also be used as appropriate.
次いで、これら基材紙層1及び調湿紙層2が乾燥する前に、この調湿紙層2の上に、紙繊維材料からなる紙料液から紙繊維を抄き取って化粧紙層3を層着形成して、乾燥処理する。   Next, before the base paper layer 1 and the humidity control paper layer 2 are dried, the paper fibers are made from the paper solution made of the paper fiber material on the humidity control paper layer 2 to make the decorative paper layer 3. Is layered and dried.
その後、化粧紙層3の最表面に撥水剤をコーティングする。本実施形態では、均一な表面処理のために、撥水剤を含むスポンジ質のローラーに回転接触させることが好ましく、最表面の繊維だけに付着させて微細な点状に撥水処理することができる。なお、含浸やスプレー法も可能である。こうして本実施形態のシート材が完成する。   Thereafter, the outermost surface of the decorative paper layer 3 is coated with a water repellent. In the present embodiment, for uniform surface treatment, it is preferable to rotationally contact a sponge-like roller containing a water repellent, and it is possible to attach only to the outermost fibers and perform water repellent treatment in the form of fine dots. it can. Impregnation and spraying methods are also possible. Thus, the sheet material of this embodiment is completed.
なお、このシート材は、靱皮繊維である麻を50%以上使用しており、かつ、天然高分子であるバインダー(所謂「ねり」)を使用して抄造されているため、「和紙」に分類されると云える。一方、洋紙は原料である木材パルプ繊維が50%以下である。   This sheet material is classified as “Japanese paper” because it uses 50% or more of hemp, a bast fiber, and is made using a natural polymer binder (so-called “neri”). It can be said that. On the other hand, wood paper contains 50% or less of wood pulp fiber as a raw material.
また、上記化粧紙層3を形成した後は、シート材全体を加圧して厚みが1〜5mmとなるようにプレス加工することができ、切断作業や継ぎ目処理等の施工や仕上げにおける簡便性も確保することができる。このプレス加工時に、C−S−H粉体を所要サイズに圧延または粉砕することもできる。更にまた、化粧紙層3の表面にエンボス加工を行うことで凹凸模様を形成して意匠性を付与することもできる。   In addition, after the decorative paper layer 3 is formed, the entire sheet material can be pressed to be 1 to 5 mm in thickness, and the convenience in construction and finishing such as cutting work and seam processing can also be achieved. Can be secured. At the time of this pressing, the C—S—H powder can be rolled or pulverized to a required size. Furthermore, an embossing process can be performed on the surface of the decorative paper layer 3 to form a concavo-convex pattern to impart design properties.
上記製造方法によれば、基材紙層1において添加された間隙調整繊維材により繊維間の隙間のサイズを小さくするため、調湿紙層2の抄造時において、微小なC−S−H粉体が基材紙層1の繊維に引っかかり易くなって、粉体の漏れ落ちが抑制され歩留りが改善される。   According to the manufacturing method described above, since the size of the gap between the fibers is reduced by the gap adjusting fiber material added in the base paper layer 1, a fine C—S—H powder is produced at the time of making the humidity control paper layer 2. The body is easily caught by the fibers of the base paper layer 1, and the leakage of the powder is suppressed and the yield is improved.
以下に、本実施形態のサンプルの種々の物性についての各試験結果を示す。   Below, each test result about the various physical properties of the sample of this embodiment is shown.
<基材紙層1の繊維材料の調湿試験>
まず、本実施形態の基材紙層1に用いる繊維材料(マニラ麻繊維、針葉樹パルプ繊維)に関する調湿試験を行った。試験方法としては、一平方メートルあたりの乾燥繊維重量が1kgとなるように抄造作成した各試験体について、23℃、50%R.H.(Relative−Humidity:相対湿度)の恒温恒湿槽中で12時間平衡にさせた後、75%R.H.に変化させ、その条件を12時間保持した後の重量を計測する「JIS A 1470−1」に準拠した湿度応答法で中湿度域の吸湿試験を採用した。
<Humidity adjustment test for fiber material of base paper layer 1>
First, the humidity control test regarding the fiber materials (manila hemp fiber, conifer pulp fiber) used for the base paper layer 1 of the present embodiment was performed. As a test method, each test specimen made by papermaking so that the dry fiber weight per square meter is 1 kg is equilibrated in a constant temperature and humidity chamber at 23 ° C. and 50% RH (Relative-Humidity) for 12 hours. After that, the humidity was changed to 75% RH, and the moisture absorption test in the middle humidity range was adopted by the humidity response method in accordance with “JIS A 1470-1” which measures the weight after maintaining the condition for 12 hours.
その結果、マニラ麻は38g/m、針葉樹パルプは36g/mであり、中湿度域で優れた調湿性能を有していることが確認された。 As a result, Manila hemp was 38 g / m 2 , and softwood pulp was 36 g / m 2 , confirming that it had excellent humidity control performance in the middle humidity range.
<基材紙層1の抄造試験>
次に、基材紙層1の抄造工程において、C−S−H粉体が歩留まりよく調湿紙層2に担持される条件を探索するため、C−S−H粉体の粒度分析と繊維材料の繊維径の計測を行った。
<Paper making test of base paper layer 1>
Next, in the paper making process of the base paper layer 1, in order to search for conditions for the C—S—H powder to be supported on the humidity-controlling paper layer 2 with a high yield, particle size analysis of the C—S—H powder and fibers The fiber diameter of the material was measured.
その結果、(1)基材紙層1から漏れ落ちなかったC−S−H粉体の粒度は1μm以上がほとんどであったこと、(2)マニラ麻繊維を50%以上配合した場合には、製造に必要な湿潤強度が確保されること、(3)また副原料として針葉樹パルプを用い、かつ、広葉樹パルプは10%以下の配合にした場合には、抄造性も良好であり、絡み合った繊維の間隙がC−S−H粉体をほとんど通過させないことが確認できた。   As a result, (1) the particle size of the C—S—H powder that did not leak from the base paper layer 1 was almost 1 μm or more, and (2) when 50% or more of Manila hemp fiber was blended, (3) In addition, when softwood pulp is used as an auxiliary material and hardwood pulp is blended at 10% or less, the papermaking property is good and the intertwined fibers It was confirmed that almost no gap of the C—S—H powder passed through.
<基材紙層1および調湿紙層2における繊維材料の配合比と吸湿量の関係>
また、基材紙層1および調湿紙層2の繊維材料とC−S−H粉体との最適な配合比率を確認するため、基材紙層1は、マニラ麻パルプを主原料(乾燥重量割合でマニラ麻90%とハウサンド社製の針葉樹パルプ10%の配合物)、その上部の調湿紙層2としてC−S−H粉体担持層を形成せしめる繊維も前記基材紙層1と同じ配合割合とし、その繊維量とC−S−H粉体との割合を、繊維量を20%〜100%の範囲で変化させる抄造試験を、天然高分子バインダー(矢沢化学工業(株)製「雅糊」)を用いて行った。また、これらを乾燥させた厚さ3.5mmの各試験体について、中湿度域(相対湿度50%〜75%)での吸湿量の測定を実施した。
<Relationship between mixing ratio of fiber material and moisture absorption in base paper layer 1 and humidity control paper layer 2>
Moreover, in order to confirm the optimal mixture ratio of the fiber material of the base paper layer 1 and the humidity control paper layer 2 and the C—S—H powder, the base paper layer 1 is made of Manila hemp pulp as a main raw material (dry weight). (The blend of 90% Manila hemp and 10% softwood pulp made by Howsand Co.), and the fibers that form the CSH powder carrying layer as the moisture conditioning paper layer 2 on the top are the same as the base paper layer 1 A papermaking test in which the ratio of the amount of fibers and the C—S—H powder is changed in a range of 20% to 100% as a blending ratio was performed using a natural polymer binder (manufactured by Yazawa Chemical Co., Ltd. “ "Magic glue"). Moreover, about each test body of thickness 3.5mm which dried these, the moisture absorption amount in the intermediate humidity range (relative humidity 50%-75%) was implemented.
また、前記の方法で得られた調湿和紙試験体に、水系のシリコーン撥水剤を用いてローラー塗布法によって撥水処理を行い、それらについても中湿度域(相対湿度50%〜75%)での吸湿量の測定を実施した。   In addition, the moisture-conditioned Japanese paper test body obtained by the above method was subjected to water repellent treatment by a roller coating method using a water-based silicone water repellent, and these were also in a medium humidity range (relative humidity 50% to 75%). Measurement of the amount of moisture absorption was performed.
具体的には、A4版のサイズに切り出した測定用のサンプルを、23℃、50%R.H.の恒温恒湿槽中で12時間平衡にさせた後、75%R.H.に変化させ、その条件を12時間保持した後の重量を計測し、重量変化とサンプル面積からから吸湿量を算出した。以下にその評価結果を示す。   Specifically, a measurement sample cut out to the size of A4 plate was equilibrated in a constant temperature and humidity chamber of 23 ° C. and 50% RH for 12 hours, and then changed to 75% RH. The weight after holding for a time was measured, and the amount of moisture absorption was calculated from the weight change and the sample area. The evaluation results are shown below.
上記〔表1〕のデータを相関分析した結果、繊維配合量と中湿度域の吸湿量には強い正の相関が確認され、近似式から相対湿度を50%から75%に変化させた際、12時間内に29g/m以上吸湿する必要がある調湿建材としての認定基準を満たすには、繊維材料とC−S−H粉体とからなる調湿和紙の乾燥総重量が1mあたり1kgである場合、パルプの配合割合は内割りで29%以上必要であることが判明した。 As a result of the correlation analysis of the data in [Table 1], a strong positive correlation was confirmed between the fiber blending amount and the moisture absorption amount in the middle humidity region, and when the relative humidity was changed from 50% to 75% from the approximate expression, In order to satisfy the certification standard as a humidity control building material that needs to absorb moisture of 29 g / m 2 or more within 12 hours, the total dry weight of the humidity control Japanese paper made of fiber material and C—S—H powder is about 1 m 2. In the case of 1 kg, it was found that the blending ratio of the pulp requires 29% or more by internal division.
また、撥水処理はローラー塗布の方法によって、撥水剤を均一に点状に付着させることができるので、吸湿性能への影響もわずかで、性能低下率は17〜18%にとどまることが確認できた。   In addition, the water repellent treatment can apply the water repellent uniformly in the form of dots by the roller coating method, so it has little effect on the hygroscopic performance and the performance degradation rate is only 17-18%. did it.
<C−S−H粉体および天然高分子バインダーの性能比較>
次に、従来技術と本発明の3つのサンプル1〜3とを比較して、無機多孔質材料やバインダー材料の違いがシート材の中湿度域の調湿性能に与える効果を検証する。まず、上記抄造試験における〔表1〕中のNo.4の配合割合(パルプの配合比50%)を基準として、同様な方法でシート状の『本発明サンプル1』を作成して、吸放湿特性を測定した。
<Performance comparison of CSH powder and natural polymer binder>
Next, by comparing the prior art and the three samples 1 to 3 of the present invention, the effect of the difference in the inorganic porous material and the binder material on the humidity control performance in the middle humidity region of the sheet material will be verified. First, in the paper making test, No. Based on the blending ratio of 4 (pulp blending ratio 50%), a sheet-like “present invention sample 1” was prepared in the same manner, and the moisture absorption / release characteristics were measured.
また、バインダー材料の違いと調湿性能について検証するために、無機多孔質体にはC−S−H粉体をそのまま使用し、バインダー材料には日信化学工業(株)製の「ビニブランTO−453N」(アクリル主成分、ガラス転移温度−26℃、有効成分48.7%)の有機エマルジョンを用いて、『本発明サンプル2』のシートを作成し、吸放湿特性の測定をした。   In addition, in order to verify the difference in the binder material and the humidity control performance, the C—S—H powder is used as it is for the inorganic porous material, and “Vinyl Blanc TO” manufactured by Nissin Chemical Industry Co., Ltd. is used as the binder material. -453N "(acrylic main component, glass transition temperature -26 ° C, active ingredient 48.7%) was used to prepare a sheet of" Invention Sample 2 ", and the moisture absorption and desorption characteristics were measured.
更にまた、無機多孔質材料の違いと調湿性能について検証するために、バインダーは天然高分子バインダーを使用し、無機多孔質体には合成ゼオライト(A型ゼオライト)であるナカライテスク(株)製の「モレキュラーシーブ4A」を使用して、『本発明サンプル3』のシートを作成し、吸放湿特性を測定した。   Furthermore, in order to verify the difference in inorganic porous materials and humidity control performance, natural binder is used as the binder, and synthetic porous zeolite (A-type zeolite) is used as the inorganic porous material. Using “Molecular Sieve 4A”, a sheet of “Invention Sample 3” was prepared and its moisture absorption / release characteristics were measured.
具体的な試験方法は、前記各サンプルを23℃、50%R.H.の恒温恒湿槽中で12時間平衡にさせて、次に75%R.H.に変化させ、12時間後の吸湿量を測定して、再び50%R.H.に戻して、12時間後の放湿量を測定した。以下にその測定結果を示す。   Specifically, each sample was equilibrated in a constant temperature and humidity chamber at 23 ° C. and 50% RH for 12 hours, then changed to 75% RH, and the moisture absorption after 12 hours was measured. After returning to 50% RH again, the moisture release amount after 12 hours was measured. The measurement results are shown below.
上記〔表2〕から、シート材が中湿度域で高い調湿性能を得るには、無機多孔質体にC−S−H粉体を使用し、バインダー材料は天然高分子バインダーを使用することが好ましいことが確認された。   From the above [Table 2], in order to obtain high humidity control performance in the medium humidity range, the sheet material should use C—S—H powder for the inorganic porous material, and use a natural polymer binder as the binder material. Was confirmed to be preferable.
<難燃性の評価試験>
次に、内装壁材には難燃性も求められることから、その基準に合致するかどうか、繊維材料とC−S−H粉体との配合比率を変えたものについての燃焼試験を行った。
<Flame retardancy evaluation test>
Next, since the interior wall material is also required to have flame retardancy, whether or not it meets the standard, a combustion test was performed on the fiber material and the C-S-H powder blending ratio changed. .
難燃性の評価方法としては、9.5mm厚の石膏ボードに壁紙用接着剤(矢沢化学工業(株)製、商品名「ウォールボンド100」)を用いて貼り付け乾燥した後、試験体を45度に傾けてライターの炎を1分間当てて燃え広がりを比較観察した。以下にその評価結果を示す。   As a method for evaluating the flame retardancy, an adhesive for wallpaper (trade name “Wall Bond 100”, manufactured by Yazawa Chemical Industry Co., Ltd.) was applied to a 9.5 mm thick gypsum board and dried. A lighter flame was applied for 1 minute at an angle of 45 degrees to observe the spread of the flame for comparison. The evaluation results are shown below.
上記〔表3〕に示した天然パルプとC−S−Hとの各配合比は、シートに難燃性をも付与し、その効果は25%の配合物でも良好であった。   Each blending ratio of natural pulp and C—S—H shown in [Table 3] above also imparted flame retardancy to the sheet, and the effect was good even with a 25% blend.
<吸放湿性能試験>
上記の難燃性測定試験において結果が良好であったNo.5の抄造条件(配合比 天然パルプ:C−S−H=75:25)で製造した撥水調湿和紙について、吸放湿性能を測定した結果を図2に示す。
<Moisture absorption / release performance test>
In the above flame retardant measurement test, the results were good. FIG. 2 shows the results of measuring the moisture absorption and desorption performance of the water-repellent moisture-conditioned Japanese paper produced under the papermaking conditions of No. 5 (mixing ratio natural pulp: C—S—H = 75: 25).
このグラフによれば、本発明品が、調湿建材としての認定基準である吸湿量29g/mの基準を上回る吸湿量を有していることがわかる。 According to this graph, it can be seen that the product of the present invention has a moisture absorption amount that exceeds the standard of the moisture absorption amount of 29 g / m 2 , which is a certification standard as a humidity control building material.
本発明は概ね上記のように構成されるが、図示の実施形態に限定されるものでは決してなく、「特許請求の範囲」の記載内において種々の変更が可能であって、例えば、基材紙層1および調湿紙層2、化粧紙層3の各主原料と副原料との重量割合および使用材料は、求める吸湿性能に応じて変更することができる。   The present invention is generally configured as described above. However, the present invention is not limited to the illustrated embodiment, and various modifications can be made within the description of “Claims”. The weight ratio of each main raw material and auxiliary raw material of the layer 1, the humidity control paper layer 2, and the decorative paper layer 3 and the material used can be changed according to the desired moisture absorption performance.
また、基材紙層1および調湿紙層2、化粧紙層3の各層の厚みの割合は、1:3:1に限らず、種々の比率に変更することもでき、これら何れのものも本発明の技術的範囲に属する。   Moreover, the ratio of the thickness of each layer of the base paper layer 1, the humidity control paper layer 2, and the decorative paper layer 3 is not limited to 1: 3: 1, and can be changed to various ratios. It belongs to the technical scope of the present invention.
本発明の実施形態の調湿和紙シート材の構造を表した破断斜視図である。It is a fracture perspective view showing the structure of the humidity control Japanese paper sheet material of the embodiment of the present invention. 本発明品の吸放湿性能を示したグラフである。It is the graph which showed the moisture absorption / release performance of this invention goods.
符号の説明Explanation of symbols
1 基材紙層
2 調湿紙層
3 化粧紙層
1 base paper layer 2 humidity control paper layer 3 decorative paper layer

Claims (12)

  1. 主原料である麻繊維材に、これと略同径であって、かつ、これと絡み性が良好な副原料の天然繊維材を混合し、さらにこれら麻繊維材および天然繊維材よりも平均繊維径および平均繊維長の小なる繊維材を間隙調整繊維材として添加して抄造された基材紙層1と;
    この基材紙層1上に層着状態に抄造され、かつ、主原料の麻繊維材と副原料の天然繊維材に対し、前記基材紙層1の繊維間隙に不透過な所定粒度の珪酸カルシウム水和物(C−S−H)粉体を混入した調湿紙層2と;
    この調湿紙層2上に層着状態に抄造されて形成され、かつ、表面に撥水加工が施された通気性を有する化粧紙層3とが積層されて一体に構成されていることを特徴とする撥水性高調湿和紙シート材。
    Hemp fiber material, which is the main raw material, is mixed with natural fiber material, which is approximately the same diameter as this, and has good entanglement, and the average fiber is higher than these hemp fiber material and natural fiber material. A base paper layer 1 made by adding a fiber material having a small diameter and average fiber length as a gap adjusting fiber material;
    Silicic acid having a predetermined particle size which is made into a layered state on the base paper layer 1 and is impervious to the fiber gaps of the base paper layer 1 with respect to the main hemp fiber material and the auxiliary natural fiber material. A humidity control paper layer 2 mixed with calcium hydrate (C—S—H) powder;
    The humidity control paper layer 2 is formed in a layered state, and a breathable decorative paper layer 3 having a water-repellent finish on the surface is laminated and integrally formed. Characteristic water-repellent harmonic wet Japanese paper sheet.
  2. 基材紙層1の麻繊維材が、乾燥重量割合で少なくとも50%以上含まれていることを特徴とする請求項1記載の撥水性高調湿和紙シート材。   The water repellent high-humidity Japanese paper sheet material according to claim 1, wherein the hemp fiber material of the base paper layer 1 is contained in a dry weight ratio of at least 50% or more.
  3. 調湿紙層2が、C−S−H粉体の乾燥重量割合が25〜70%で、麻繊維材と針葉樹パルプ繊維と広葉樹パルプ繊維からなる天然パルプ繊維が少なくとも乾燥重量割合が30%以上含まれ、それらが天然高分子バインダーによって結合形成されていることを特徴とする請求項1または2記載の撥水性高調湿和紙シート材。   The moisture conditioning paper layer 2 has a dry weight ratio of C-S-H powder of 25 to 70%, and a natural pulp fiber composed of hemp fiber material, softwood pulp fiber and hardwood pulp fiber is at least a dry weight ratio of 30% or more The water repellent high-humidity Japanese paper sheet material according to claim 1, wherein the water-repellent high-humidity Japanese paper sheet material is contained and bonded with a natural polymer binder.
  4. 化粧紙層3が、乾燥重量割合で麻繊維材80〜90%と針葉樹パルプを主原料とする繊維が10〜20%の乾燥重量割合で混合・抄造されていることを特徴とする請求項1〜3の何れか一つに記載の撥水性高調湿和紙シート材。   The decorative paper layer 3 is formed by mixing and making 80 to 90% of hemp fiber material and 10 to 20% of a dry weight ratio of fibers composed mainly of softwood pulp in a dry weight ratio. The water repellent harmonic moisture Japanese paper sheet material as described in any one of -3.
  5. 化粧紙層3の表面凹凸の頭頂部において、微細な点状に撥水剤が付着加工されていることを特徴とする請求項1〜4の何れか一つに記載の撥水性高調湿和紙シート材。   5. The water-repellent high-humidity Japanese paper sheet according to claim 1, wherein a water-repellent agent is attached to the top of the uneven surface of the decorative paper layer 3. Wood.
  6. 調湿紙層2のC−S−H粉体が、粒径1μm以上で、かつ、加熱脱水処理されたものであることを特徴とする請求項1〜5の何れか一つに記載の撥水性高調湿和紙シート材。   The C—S—H powder of the humidity-controlling paper layer 2 has a particle size of 1 μm or more and is subjected to heat dehydration treatment. Aqueous high-humidity Japanese paper sheet material.
  7. 基材紙層1および調湿紙層2における主原料の麻繊維材がマニラ麻繊維であることを特徴とする請求項1〜6の何れか一つに記載の撥水性高調湿和紙シート材。   The water repellent high-humidity Japanese paper sheet material according to any one of claims 1 to 6, wherein the hemp fiber material of the main raw material in the base paper layer 1 and the humidity control paper layer 2 is Manila hemp fiber.
  8. 基材紙層1および調湿紙層2における副原料の天然繊維材が針葉樹パルプ繊維であることを特徴とする請求項1〜7の何れか一つに記載の撥水性高調湿和紙シート材。   The water-repellent high-humidity humidified Japanese paper sheet material according to any one of claims 1 to 7, wherein the natural fiber material of the auxiliary material in the base paper layer 1 and the humidity control paper layer 2 is a softwood pulp fiber.
  9. 基材紙層1における間隙調整繊維材が広葉樹パルプ繊維であることを特徴とする請求項1〜8の何れか一つに記載の撥水性高調湿和紙シート材。   The water repellent high-humidity Japanese paper sheet material according to any one of claims 1 to 8, wherein the gap adjusting fiber material in the base paper layer 1 is hardwood pulp fiber.
  10. 基材紙層1および調湿紙層2、化粧紙層3に、それぞれ天然高分子から成る植物性バインダー材料が混合されていることを特徴とする請求項1〜9の何れか一つに記載の撥水性高調湿和紙シート材。   The vegetable binder material which consists of a natural polymer, respectively is mixed with the base paper layer 1, the humidity-control paper layer 2, and the decorative paper layer 3, Each of Claim 1-9 characterized by the above-mentioned. Water repellent high-quality moisture Japanese paper sheet material.
  11. 化粧紙層3の主原料が麻繊維材であることを特徴とする請求項1〜10の何れか一つに記載の撥水性高調湿和紙シート材。   The water-repellent harmonic moisture Japanese paper sheet material according to any one of claims 1 to 10, wherein a main raw material of the decorative paper layer 3 is hemp fiber material.
  12. 麻繊維材を主原料とし、これと略同径であって、かつ、これと絡み性の良好な天然繊維材を副原料として、植物性バインダーとともに水中に遊離状に分散混合させ、更に前記麻繊維材および天然繊維材よりも平均繊維径および平均繊維長の小なる繊維材を間隙調整繊維材として添加して基材紙料液を調製し、この基材紙料液から前記各繊維を含む基材紙層を抄き取った後、この抄き取った前記基材紙層が乾燥する前に、主原料の麻繊維材および副原料の天然繊維材とを含む紙料液に、前記基材紙層の繊維間隙に不透過な所定粒度の珪酸カルシウム水和物(C−S−H)粉体を混入して調製した調湿紙料液を抄き取って調湿紙層を層着せしめ、ついで、これら基材紙層および調湿紙層が乾燥する前に、この調湿紙層の上に、紙繊維材料からなる紙料液から紙繊維を抄き取って化粧紙層を層着形成して乾燥処理し、然る後、前記化粧紙層の表面に撥水加工を施すことを特徴とする撥水性高調湿和紙シート材の製造方法。   A hemp fiber material is used as a main raw material, and a natural fiber material having substantially the same diameter as this and having good entanglement properties is used as a secondary raw material, and is dispersed and mixed in water together with a vegetable binder. A fiber material having a smaller average fiber diameter and average fiber length than the fiber material and natural fiber material is added as a gap adjusting fiber material to prepare a base material liquid, and each of the fibers is included from the base material liquid After the base paper layer is cut off, before the base paper layer thus picked up is dried, the base material layer contains a hemp fiber material as a main material and a natural fiber material as a sub raw material. The humidity-controlling paper layer prepared by mixing calcium silicate hydrate (CSH) powder of a predetermined particle size that is impervious to the fiber gaps of the paperboard layer is layered to form a humidity-controlling paper layer. And then, before the base paper layer and the humidity control paper layer are dried, on the humidity control paper layer, it is made of a paper fiber material. A water-repellent, high-humidity Japanese paper sheet, wherein paper fiber is made from a liquid, and a decorative paper layer is formed and dried, and then the surface of the decorative paper layer is subjected to a water-repellent treatment. A method of manufacturing the material.
JP2008173418A 2008-07-02 2008-07-02 Water-repellent, highly humidity-conditioning japanese paper sheet material and method for producing the same Pending JP2010013753A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016135463A1 (en) * 2015-02-24 2016-09-01 Filer, Annabelle Agricultural fibre-based paper
WO2017081600A1 (en) * 2015-11-09 2017-05-18 Stora Enso Oyj Active moisture control material for packaging
WO2018138964A1 (en) * 2017-01-30 2018-08-02 エステー株式会社 Deodorizing sheet and deodorizing method
CN110528305A (en) * 2019-09-04 2019-12-03 齐鲁工业大学 A kind of preparation method of the liquid crystal glass base feeding spaced papers of " seersucker " structure

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016135463A1 (en) * 2015-02-24 2016-09-01 Filer, Annabelle Agricultural fibre-based paper
WO2017081600A1 (en) * 2015-11-09 2017-05-18 Stora Enso Oyj Active moisture control material for packaging
WO2018138964A1 (en) * 2017-01-30 2018-08-02 エステー株式会社 Deodorizing sheet and deodorizing method
CN110528305A (en) * 2019-09-04 2019-12-03 齐鲁工业大学 A kind of preparation method of the liquid crystal glass base feeding spaced papers of " seersucker " structure

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