JP2012174834A - Electromagnetic wave suppression sheet - Google Patents
Electromagnetic wave suppression sheet Download PDFInfo
- Publication number
- JP2012174834A JP2012174834A JP2011034312A JP2011034312A JP2012174834A JP 2012174834 A JP2012174834 A JP 2012174834A JP 2011034312 A JP2011034312 A JP 2011034312A JP 2011034312 A JP2011034312 A JP 2011034312A JP 2012174834 A JP2012174834 A JP 2012174834A
- Authority
- JP
- Japan
- Prior art keywords
- electromagnetic wave
- sheet
- suppression sheet
- wave suppression
- wet strength
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000001629 suppression Effects 0.000 title claims abstract description 23
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 18
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 8
- 229920001732 Lignosulfonate Polymers 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 abstract description 8
- 239000000460 chlorine Substances 0.000 abstract description 8
- 238000012805 post-processing Methods 0.000 abstract description 6
- 238000005470 impregnation Methods 0.000 abstract description 5
- 238000005520 cutting process Methods 0.000 abstract description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract 1
- 229920005610 lignin Polymers 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 8
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000701 coagulant Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 229920001131 Pulp (paper) Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000007429 general method Methods 0.000 description 4
- 239000013054 paper strength agent Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000006247 magnetic powder Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000013055 pulp slurry Substances 0.000 description 1
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
Images
Landscapes
- Paper (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
本発明は、電磁ノイズを抑制するためのシートに関するものである。 The present invention relates to a sheet for suppressing electromagnetic noise.
近年のパーソナルコンピューター（以下、ＰＣ）をはじめとする各種電子機器の高度化や携帯電話に代表される移動体通信機器の普及には著しいものがある。しかしながら、これらの電子機器や通信機器では、高性能化を実現させるため電子部品を高密度に実装させるが故に電子機器内部での電磁障害を発生させたり、これらの機器から放射された電磁ノイズにより他の機器に誤作動を生じさせたり、人体に影響を及ぼすといった危険性も指摘されてきている。
又、例えばＰＣではＧＨz帯で動作するＭＰＵが主流になってきているため、発生する電磁ノイズの周波数も高くなる傾向にあり、１ＧＨzを越えるような放射電磁ノイズが問題になってきている。
In recent years, various electronic devices such as personal computers (hereinafter referred to as PCs) have become more sophisticated and mobile communication devices represented by mobile phones have been widely used. However, in these electronic devices and communication devices, electronic components are mounted at a high density in order to achieve high performance, so that electromagnetic interference occurs inside the electronic devices, or electromagnetic noise radiated from these devices. There are also dangers that cause malfunctions in other devices and affect the human body.
In addition, for example, MPUs operating in the GHz band are becoming mainstream in PCs, so the frequency of generated electromagnetic noise tends to increase, and radiated electromagnetic noise exceeding 1 GHz has become a problem.
このような電磁ノイズは基本的には回路設計にて十分考慮されるが、どうしても発生を防げない場合は、一般に「ノイズ抑制シート」と呼ばれるシートを使用する。 Basically, such electromagnetic noise is sufficiently considered in circuit design, but if it cannot be prevented by any means, a sheet generally called “noise suppression sheet” is used.
ノイズ抑制シートには、樹脂に磁性金属片を混合させたものをシート化したものや、軟磁性粉末と合成ゴムを混合させたものをシート化したもの等が知られている。又、近年では、難燃化機能をつけたタイプや、ハロゲンフリータイプなどの要望が高まっており、各種提案されてきている。又、各種電子機器や通信機器においては、小型化，軽量化という顧客ニーズの流れがあるが、特に、上述したようなノイズ抑制シートでは、密度の大きな磁性金属片や軟磁性粉末を大量に入れて機能を発現させるため、厚さや重さの点で、顧客のニーズである、各種電子機器の小型化や軽量化といった点で問題があった。 As the noise suppression sheet, a sheet obtained by mixing a magnetic metal piece with a resin, a sheet obtained by mixing a soft magnetic powder and a synthetic rubber, and the like are known. In recent years, the demand for a flame retardant type and a halogen-free type has been increased, and various proposals have been made. In various electronic devices and communication devices, there is a flow of customer needs for downsizing and weight reduction. In particular, in the noise suppression sheet as described above, a large amount of magnetic metal pieces and soft magnetic powder are put in large quantities. In order to express the functions, there are problems in terms of thickness and weight in terms of customer needs, such as downsizing and weight reduction of various electronic devices.
これらの問題を解決するために、例えば特許文献１（特開昭６３−２８８２９８）、特許文献２（特開２００９−２７７７３６）や特許文献３（特開２０１０−４０７３０）のように、セルロース繊維等に繊維状カーボンを内添したような紙ベースのノイズ抑制シートが提案されている。紙ベース基材は、単に厚さや重さの点のみでなく、カーボンニュートラルの観点からも好ましい。しかしながら、このような紙ベースのノイズ抑制シートは、可燃性のセルロースが含まれているため、燃えやすく、又、裁断する際に紙粉のような脱落物が発生してしまうという問題があった。 In order to solve these problems, for example, as described in Patent Document 1 (JP-A 63-288298), Patent Document 2 (JP-A 2009-277736), and Patent Document 3 (JP-A 2010-40730), cellulose fibers, etc. A paper-based noise suppression sheet in which fibrous carbon is internally added has been proposed. Paper base substrates are preferred not only in terms of thickness and weight, but also from the viewpoint of carbon neutral. However, since such a paper-based noise suppression sheet contains combustible cellulose, it is easy to burn, and there is a problem in that a falling matter such as paper dust is generated when cutting. .
難燃性の付与については、難燃剤を内添したり、含浸等の後加工をしたりする方法が、特許文献２や特許文献３や特許文献４（特開２００９−１９４３４１）に記載されている。しかしながら、これらのシートを扱ったり、裁断する際に問題となる脱落物に関しては、特許文献１〜４には何ら記載されていない。この脱落物の防止には、例えば、無塵紙の製造方法が参考になる。例えば、特許文献５（特昭開６０−１６７９９６）では紙に特定の高分子物質を含浸させることによって塵を抑えている。
このように、セルロース繊維を主体としたノイズ抑制シートでは、難燃性付与や脱落異物の防止を実施する必要があり、そのためには難燃性や脱落異物対策として、樹脂含浸等の後加工が必須となる。
For imparting flame retardancy, methods of internally adding a flame retardant or post-processing such as impregnation are described in Patent Document 2, Patent Document 3, and Patent Document 4 (Japanese Patent Laid-Open No. 2009-194341). Yes. However, there is no description in
As described above, in the noise suppression sheet mainly composed of cellulose fibers, it is necessary to impart flame retardancy and prevent foreign matter from falling off. To that end, post-processing such as resin impregnation is required as a measure against flame retardancy and falling off foreign matter. Required.
セルロース繊維を主体としたシート原紙に含浸等の後加工性を付与するには、シート原紙に十分な湿潤強度を付与する必要があり、方法としては、メラミンホルムアルデヒド系、尿素ホルムアルデヒド系、ポリアミドポリアミンエピクロロヒドリン系の湿潤紙力剤を内添する方法が一般的である。しかし、近年、メラミンホルムアルデヒド系、尿素ホルムアルデヒド系湿潤紙力剤については、遊離ホルムアルデヒドが発生し、作業環境の悪化を招くことから、ポリアミドポリアミンエピクロロヒドリン系湿潤紙力剤（以下、ＰＡＥと表する）への切り替えが進んでいる。又、ＰＡＥは、広範囲なｐＨ領域で効果を発現できる等、機能的な面でも優れており、中性紙の生産が主である現状では、国内で使用されている湿潤紙力剤の８５％はＰＡＥと言われている(非特許文献１)。 In order to impart post-processing properties such as impregnation to a sheet base paper mainly composed of cellulose fibers, it is necessary to provide the sheet base paper with sufficient wet strength. Methods include melamine formaldehyde, urea formaldehyde, polyamide polyamine epitaxy. A method of internally adding a chlorohydrin-based wet paper strength agent is common. However, in recent years, melamine formaldehyde-based and urea formaldehyde-based wet paper strength agents generate free formaldehyde, which leads to deterioration of the working environment. Switch to (Yes) is progressing. In addition, PAE is excellent in terms of functionality, such as being able to exhibit effects in a wide pH range, and in the current situation where neutral paper is mainly produced, 85% of wet paper strength agents used in Japan. Is said to be PAE (Non-Patent Document 1).
しかしながら、このＰＡＥ中には塩素（ハロゲン）が含まれているため、上記したような、今後、益々要望が高くなるであろうハロゲンフリーのノイズ抑制シートに
用いるのは好ましくない。ＰＡＥを用いなくとも後加工に必要な湿潤強度を付与してやる必要性がある。
However, since this PAE contains chlorine (halogen), it is not preferable to use it for a halogen-free noise suppression sheet that will become increasingly demanded in the future as described above. There is a need to give wet strength necessary for post-processing without using PAE.
本発明は、従来の紙ベースのノイズ抑制シートの欠点であった、湿潤強度を改善し、且つ、ハロゲンフリー（今回の構成では、塩素量を減らすことを意味する）となるような、電磁波抑制シートを提供することを課題とする。 The present invention is a disadvantage of the conventional paper-based noise suppression sheet, which suppresses electromagnetic waves that improve wet strength and is halogen-free (in this configuration, it means that the amount of chlorine is reduced). It is an object to provide a sheet.
本発明者らは、かかる課題を解決するため鋭意検討した結果、電磁波抑制シートを製造する際、リグニンスルホン酸塩とポリビニルアミンを併用することによって、課題を解決できることを見出し、本発明に到達した。 As a result of intensive studies to solve such problems, the present inventors have found that the problem can be solved by using lignin sulfonate and polyvinylamine together when producing an electromagnetic wave suppression sheet, and the present invention has been achieved. .
すなわち本発明によれば、以下の製造方法が提案される。
（１）リグニンスルホン酸塩で分散されたカーボンナノチューブとセルロース繊維とから成り、ポリビニルアミンを併用することを特徴とする湿潤強度０.４０kN/m以上、体積抵抗率が１.００Ω・ｃｍ以下の電磁波抑制シート
（２）リグニンスルホン酸塩の添加率が、カーボンナノチューブに対し、６０〜１５０％であり、且つ、ポリビニルアミンの添加率が、セルロース繊維に対し、０.５〜３.０％であることを特徴とする、（１）の電磁波抑制シート
That is, according to the present invention, the following manufacturing method is proposed.
(1) It consists of carbon nanotubes and cellulose fibers dispersed with lignin sulfonate, and is used in combination with polyvinylamine. It has a wet strength of 0.40 kN / m or more and a volume resistivity of 1.00 Ω · cm or less. Electromagnetic wave suppression sheet (2) The addition rate of lignin sulfonate is 60 to 150% with respect to carbon nanotubes, and the addition rate of polyvinylamine is 0.5 to 3.0% with respect to cellulose fibers. The electromagnetic wave suppression sheet according to (1), wherein
本発明によれば、紙粉対策や難燃性を付与するための後加工工程でも断紙し難い十分な湿潤強度を持ち、ハロゲン含有率が少ない、電磁波ノイズ抑制効果に優れた、電磁波抑制シートが提供される。
According to the present invention, an electromagnetic wave suppression sheet having sufficient wet strength that is difficult to break even in a post-processing step for imparting countermeasures against paper dust and flame retardancy, low halogen content, and excellent electromagnetic noise suppression effect. Is provided.
以下、本発明の製造法を詳細に説明する。
本発明の電磁波抑制シートは、セルロース繊維、カーボンナノチューブ（分散剤で分散されたもの）、凝結剤、カチオン性ポリマー等から成るスラリーを湿式抄造するものである。
用いられるセルロース系繊維を主として用いるが、特に限定するものではなく、各種木材パルプ（機械パルプ，化学パルプ，セミケミカルパルプ）や非木材繊維が使用できる。ＮＢＫＰ、ＬＢＫＰはシート強度が高く出るため好ましい。更には、ＥＣＦ（Elemental Chlrine Free）パルプやＴＣＦ（Total Chlorine Free）パルプの使用は特に好ましい。又、物性を阻害しない範囲で、合成繊維や半合成繊維を併用しても良い。上記のセルロース繊維は、物性を阻害しない限り、任意な配合で用いることができる。これらのセルロース繊維は、固形分濃度３〜５％になるようにパルパーで離解する。このパルプスラリーをリファイナーやビーターを用いてカナディアンショッパーフリーネス（ＣＳＦ）で６５０〜３００mｌに叩解する。
Hereinafter, the production method of the present invention will be described in detail.
The electromagnetic wave suppression sheet according to the present invention is a wet papermaking slurry made of cellulose fibers, carbon nanotubes (dispersed with a dispersant), a coagulant, a cationic polymer, and the like.
Cellulose fibers used are mainly used, but are not particularly limited, and various wood pulps (mechanical pulp, chemical pulp, semi-chemical pulp) and non-wood fibers can be used. NBKP and LBKP are preferable because of high sheet strength. Furthermore, the use of ECF (Elemental Chlrine Free) pulp or TCF (Total Chlorine Free) pulp is particularly preferable. Further, synthetic fibers and semi-synthetic fibers may be used in combination as long as the physical properties are not impaired. The above cellulose fibers can be used in any combination as long as the physical properties are not impaired. These cellulose fibers are disaggregated with a pulper so that the solid content concentration is 3 to 5%. This pulp slurry is beaten to 650-300 ml with Canadian shopper freeness (CSF) using a refiner or beater.
カーボンナノチューブ（以下、ＣＮＴと示す）の製法には、ＣＶＤ法，レーザー蒸発法，アーク放電法等があり、何れの製法で製造されたＣＮＴも使用できるが、商業的にはマルチウォールを使用した方が良い。又、繊維径は小さく、アスペクト比の大きい方が良い。ワイヤー上での濾水性が著しく悪くなるような場合等は、炭素繊維等を混抄しても構わない。 Carbon nanotube (hereinafter referred to as CNT) production methods include CVD, laser evaporation, arc discharge, etc., and CNTs produced by any of these production methods can be used, but a multiwall was used commercially. Better. Also, the fiber diameter should be small and the aspect ratio should be large. When the drainage on the wire is remarkably deteriorated, carbon fiber or the like may be mixed.
ＣＮＴは非常に凝集し易い性質をもっており、市販品をそのまま使用しても、電磁波抑制効果を得ることはできないため、ＣＮＴの分散体を得る必要がある。ＣＮＴを分散媒に分散させる方法は、様々な分散法が提案されている。本報では、分散剤として、リグニンスルホン酸塩を用い、超音波ホモジナイザー等の分散装置にてＣＮＴの分散液を調整する。 CNT has a property of being easily aggregated, and even if a commercially available product is used as it is, an electromagnetic wave suppressing effect cannot be obtained. Therefore, it is necessary to obtain a CNT dispersion. Various dispersion methods have been proposed for dispersing CNTs in a dispersion medium. In this report, lignin sulfonate is used as a dispersing agent, and a dispersion of CNTs is prepared by a dispersing device such as an ultrasonic homogenizer.
分散装置でＣＮＴを分散させる場合、あまり時間をかけ過ぎると、ＣＮＴがちぎれたり、構造的なダメージを受けるため、電磁波抑制効果を低下させることがある。又、湿式抄紙でＣＮＴを用いる場合は、ＣＮＴをあまり分散させ過ぎると、ＣＮＴのワイヤー上の歩留まりが低下し、電磁波抑制効果を妨げてしまう。更に、ＣＮＴの歩留まりを上げるために、歩留まり剤等の薬品を過剰添加し過ぎると、ＣＮＴが凝集してしまい、結局、十分な電磁波制能が得られない。よって適度な分散状態を維持する必要がある。
例えば、実施例１に記載しているような、レーザー回折／散乱式粒粒子径測定装置（ＬＡ―９５０Ｖ２；堀場製作所製）を使用した場合は、メジアン径で０.２〜８０μm程度が好ましい。
When CNTs are dispersed with a dispersing device, if too much time is taken, CNTs are torn off or structural damage is caused, which may reduce the electromagnetic wave suppression effect. In addition, when CNT is used in wet papermaking, if the CNT is dispersed too much, the yield of the CNT on the wire is lowered and the electromagnetic wave suppressing effect is hindered. Furthermore, if a chemical such as a retention agent is added excessively in order to increase the yield of CNTs, the CNTs aggregate, and eventually sufficient electromagnetic wave control cannot be obtained. Therefore, it is necessary to maintain an appropriate dispersion state.
For example, when a laser diffraction / scattering particle size measuring apparatus (LA-950V2; manufactured by HORIBA, Ltd.) as described in Example 1 is used, the median diameter is preferably about 0.2 to 80 μm.
使用する分散剤の量は、ＣＮＴに対し、６０〜１５０％が好ましい。６０％よりも少ないとＣＮＴが十分分散せず、体積抵抗値が高くなってしまう。又、１５０％よりも多いと、体積抵抗値が高くなってしまったり、湿潤強度が低くなってしまう。体積抵抗値が高くなってしまうと、電磁波抑制能も十分発現しない。 The amount of the dispersant used is preferably 60 to 150% with respect to CNT. If it is less than 60%, CNTs are not sufficiently dispersed and the volume resistance value becomes high. On the other hand, if it exceeds 150%, the volume resistance value becomes high and the wet strength becomes low. If the volume resistance value becomes high, the electromagnetic wave suppressing ability is not sufficiently exhibited.
本願では、塩素フリーであるポリビニルアミン類をさらに用いる。これにより、十分な湿潤強度を持ち、ハロゲン含有率が少ない電磁波抑制シートを得ることができる。ポリビニルアミン類の使用量としては、セルロース繊維に対して、０.５％〜３.０％が好ましい。０.５％以下になると十分な湿潤強度は得られない。又、３.０％以上になるとＣＮＴが過凝集して、体積抵抗値が高くなってしまう。
本願の十分な湿潤強度とは、後処理工程において、難燃性の付与、樹脂含浸等に支障のない湿潤強度をいう。実施例に記載した方法により測定した場合、０．４０ｋＮ/ｍ以上である。
In the present application, polyvinylamines that are chlorine-free are further used. Thereby, an electromagnetic wave suppression sheet having sufficient wet strength and a low halogen content can be obtained. As usage-amount of polyvinylamine, 0.5%-3.0% are preferable with respect to a cellulose fiber. If it is 0.5% or less, sufficient wet strength cannot be obtained. On the other hand, if it is 3.0% or more, CNTs are excessively agglomerated and the volume resistance value becomes high.
The sufficient wet strength of the present application refers to wet strength that does not hinder the provision of flame retardancy and resin impregnation in the post-treatment process. When measured by the method described in the examples, it is 0.40 kN / m or more.
塩素の含有量は、試料燃焼-イオンクロマトグラフ法（ＢＳ ＥＮ１４５８２）に準拠し測定を行った。シート中の塩素の含有量は、出来るだけ低いほうが好ましが、３００ｐｐｍ以下、好ましくは２００ｐｐｍ以下、さらに好ましくは１５０ｐｐｍ以下である。 The chlorine content was measured according to the sample combustion-ion chromatography method (BS EN 14582). The chlorine content in the sheet is preferably as low as possible, but is 300 ppm or less, preferably 200 ppm or less, and more preferably 150 ppm or less.
本願では、必要に応じて凝結剤を用いることができる。凝結剤としては、硫酸バンド、塩化アルミ、ポリ塩化アルミ等の無機凝結剤や有機凝結剤を用いる。これらの薬品は、セルロース繊維（含微細繊維）、ＣＮＴ、その他の薬品を電荷中和し、それらを凝結させて、シート中に留め、ワイヤーやロール等の汚れを防止する効果がある。 In the present application, a coagulant can be used as necessary. As the coagulant, an inorganic coagulant such as sulfuric acid band, aluminum chloride, polyaluminum chloride or an organic coagulant is used. These chemicals have the effect of neutralizing the charge of cellulose fibers (fine fibers), CNTs, and other chemicals, condensing them, and retaining them in the sheet to prevent stains such as wires and rolls.
ｐＨ調整剤については、アルミン酸ナトリウム、水酸化ナトリウム等が用いられる。 As the pH adjuster, sodium aluminate, sodium hydroxide, or the like is used.
上記、セルロース系繊維の叩解液、リグニンスルホン酸塩で分散したＣＮＴ分散液、及びポリビニルアミン類、必要応じて凝結剤を混合したスラリーは、固形分０．０２〜２．０％程度に希釈された後、湿式抄紙法により製造される。このとき、更に凝集剤を用いることもできる。凝集剤は、スラリーを０．０２〜２．０％程度に希釈された後に添加することが好ましい。凝集剤としては、ポリアクリルアミド，ポリエチレンオキサイド等が挙げられる。 The above slurry of cellulose fiber, CNT dispersion dispersed with lignin sulfonate, and polyvinylamines, and a slurry mixed with a coagulant if necessary, are diluted to a solid content of about 0.02 to 2.0%. Then, it is manufactured by a wet papermaking method. At this time, a flocculant can also be used. The flocculant is preferably added after the slurry is diluted to about 0.02 to 2.0%. Examples of the aggregating agent include polyacrylamide and polyethylene oxide.
本発明の実施例における評価方法は下記の通りである。 Evaluation methods in the examples of the present invention are as follows.
（１）湿潤引張強度
ＪＩＳ Ｐ８１３５の一般法に準じて、測定を行った。シートの湿潤引張強度は０.４０kN/m以上が好ましい。
(1) Wet tensile strength Measurement was performed according to the general method of JIS P8135. The wet tensile strength of the sheet is preferably 0.40 kN / m or more.
（２）乾燥引張強度
ＪＩＳ P８１１３の一般法に準じて、測定を行った。
(2) Dry tensile strength Measurement was performed according to the general method of JIS P8113.
（３）米坪
ＪＩＳ Ｐ８１２４の一般法に準じて、測定を行った。
(3) Measurement was carried out in accordance with the general method of JIS P8124.
（４）厚さ
ＪＩＳ Ｐ８１１８の一般法に準じて、測定を行った。
(4) Thickness Measurement was performed according to the general method of JIS P8118.
（５）シート中塩素量
試料燃焼-イオンクロマトグラフ法（ＢＳ ＥＮ１４５８２）に準拠し測定を行った。
(5) Chlorine content in sheet The measurement was performed according to the sample combustion-ion chromatograph method (BS EN 14582).
（６）体積抵抗率
試料を巾１.５ｃｍ，長さ１５ｃｍに切り出し、デジタルマルチメーター７３３０２（横河メータ＆インスツルメンツ社製）を用いて、テスターリード（二本）の先端部の一つを該試料の表面に接触させ、もう一方のテスターリードの先端を該試料の裏面に接触させて、二本のテスターリードの間隔を１０ｃｍとり、抵抗値を測定した。この抵抗値から以下の式を用いて、体積抵抗率を算出した。
体積抵抗率＝抵抗値×試料巾×試料厚さ／テスターリード間隔
体積抵抗率としては、１.００cm・Ω以下が好ましい。
(6) Volume resistivity
A sample is cut to a width of 1.5 cm and a length of 15 cm, and one end of the tester leads (two) is brought into contact with the surface of the sample using a digital multimeter 73302 (manufactured by Yokogawa Meter & Instruments). The tip of the other tester lead was brought into contact with the back surface of the sample, the distance between the two tester leads was 10 cm, and the resistance value was measured. From this resistance value, the volume resistivity was calculated using the following equation.
Volume resistivity = resistance value × sample width × sample thickness / tester lead interval
The volume resistivity is preferably 1.00 cm · Ω or less.
（７）伝送減衰率
電磁波抑制能の評価には、マイクロストリップライン法に基づいた伝送減衰率（＝Ｒtp）の測定を実施した（ＩＥＣ６２３３３−２ ４．３）。
(7) Transmission attenuation rate For the evaluation of the electromagnetic wave suppression ability, the transmission attenuation rate (= Rtp) based on the microstrip line method was measured (IEC 62333-2 4.3).
実施例１
リグニンスルホン酸ナトリウム（サンエキスＰ２５２；日本製紙ケミカル社製）の２.０％水溶液を調整し、その中にカーボンナノチューブ（以下、ＣＮＴ）：ＶＧＣＦ−Ｘ（昭和電工製）を加え、ＣＮＴの２.０％液とした。このＣＮＴの２.０％溶液を超音波ホモジナイザー（ＵＳ−６００ＦＣＡＴ；日本精機製）で９０ｍｉｎ処理し（振幅４０μm）、ＣＮＴ分散液を得た。この分散液をレーザー回折／散乱式粒粒子径測定装置（ＬＡ−９５０Ｖ２；堀場製作所製）で測定したところ、ＣＮＴのメジアン径は０.３５μｍであった。
セルロース繊維として、叩解度４８７ｍｌのＬＢＫＰ（ＥＣＦパルプ）を４.０％懸濁液とし、この懸濁液に、該ＣＮＴ分散液を該ＬＢＫＰ：１００重量部に対して、ＣＮＴが１０重量部となるように加えた。更に、ポリビニルアミン（カチオファストＶＦＨ；ＢＡＳＦ社製）を１.０重量部、硫酸バンド６重量部を加えた後、アルミン酸ナトリウムを加えて、ｐＨ７.３のスラリーを調成した。
この、スラリーを水で０.５％に希釈した後、アニオン性アクリルアミド系凝集剤（ＦＡ−２３０；ハイモ社製を０.０３重量部添加し、速やかに角型手抄きにて手抄きを行い、米坪８５.３ｇ/ｍ２，厚さ０.１２０ｍｍのシートを得た。
Example 1
A 2.0% aqueous solution of sodium lignin sulfonate (Sun Extract P252; manufactured by Nippon Paper Chemicals Co., Ltd.) was prepared, and carbon nanotubes (hereinafter referred to as CNT): VGCF-X (manufactured by Showa Denko) were added thereto. 0.0% solution was obtained. This CNT 2.0% solution was treated with an ultrasonic homogenizer (US-600FCAT; manufactured by Nippon Seiki Co., Ltd.) for 90 min (amplitude 40 μm) to obtain a CNT dispersion. When this dispersion was measured with a laser diffraction / scattering particle size measuring device (LA-950V2; manufactured by Horiba, Ltd.), the median diameter of CNT was 0.35 μm.
As a cellulose fiber, LBKP (ECF pulp) having a beating degree of 487 ml was made into a 4.0% suspension, and the suspension was mixed with 10 parts by weight of CNT with respect to 100 parts by weight of the CNT dispersion. It was added to become. Furthermore, after adding 1.0 part by weight of polyvinylamine (Cathiofast VFH; manufactured by BASF) and 6 parts by weight of a sulfuric acid band, sodium aluminate was added to prepare a slurry of pH 7.3.
After the slurry was diluted to 0.5% with water, 0.03 part by weight of an anionic acrylamide-based flocculant (FA-230; manufactured by Hymo Co., Ltd.) was added, and the paper was quickly hand-drawn by square hand-drawing. To obtain a sheet having a weight of 85.3 g / m 2 and a thickness of 0.120 mm.
実施例２
実施例１における、リグニンスルホン酸ナトリウムの代わりに、高純度部分脱スルホンリグニンスルホン酸ナトリウム（バニレックスＮ；日本製紙ケミカル社製）を使用する以外は、実施例１と同様に実施し、米坪９２.６ｇ/ｍ２，厚さ０.１２６ｍｍのシートを得た。
Example 2
The same procedure as in Example 1 was used, except that high-purity partially desulfurized sodium lignin sulfonate (Vanilex N; manufactured by Nippon Paper Chemicals Co., Ltd.) was used instead of sodium lignin sulfonate in Example 1. A sheet having a thickness of 0.6 g / m 2 and a thickness of 0.126 mm was obtained.
比較例１
実施例１における、リグニンスルホン酸ナトリウムの代わりに、ナフタレンスルホン酸ホルマリン縮合物ナトリウム（デモールＮ；花王社製）を使用する以外は、実施例１と同様に実施し、米坪８８.３ｇ/ｍ２，厚さ０.１２７ｍｍのシートを得た。湿潤強度が不十分であった。
Comparative Example 1
The same procedure as in Example 1 was conducted except that sodium naphthalene sulfonate formalin condensate (Demol N; manufactured by Kao Corporation) was used in place of sodium lignin sulfonate in Example 1, and 88.3 g / m 2 2. A sheet having a thickness of 0.127 mm was obtained. The wet strength was insufficient.
比較例２
実施例１における、リグニンスルホン酸ナトリウムの代わりに、ポリスチレンスルホン酸ナトリウム（ＰＳ−５０；東ソー有機化学製）を使用する以外は、実施例１と同様に実施し、米坪８４.３ｇ/ｍ２，厚さ０.１３２ｍｍの電磁波抑制材を得た。湿潤強度及び体積抵抗値が不十分であった。
Comparative Example 2
The same procedure as in Example 1 was performed except that sodium polystyrene sulfonate (PS-50; manufactured by Tosoh Organic Chemical Co., Ltd.) was used instead of sodium lignin sulfonate in Example 1, and 84.3 g / m 2 of rice tsubo. An electromagnetic wave suppressing material having a thickness of 0.132 mm was obtained. The wet strength and volume resistance value were insufficient.
比較例３
実施例１における、ポリビニルアミンの代わりに、ポリアミドポリアミンエピクロルヒドリン樹脂系湿潤紙力剤（ＳＲ−６６１５；田岡化学工業製）を使用する以外は、実施例１と同様に実施し、米坪９０.７ｇ/ｍ２，厚さ０.１３５ｍｍのシートを得た。湿潤強度が不十分であり、塩素量が多かった。
Comparative Example 3
The same procedure as in Example 1 was performed except that a polyamide polyamine epichlorohydrin resin-based wet paper strength agent (SR-6615; manufactured by Taoka Chemical Industries) was used instead of polyvinylamine in Example 1, and 90.7 g of rice tsubo A sheet having a thickness of 0.135 mm / m 2 was obtained. The wet strength was insufficient and the amount of chlorine was large.
上記の実施例１〜２、比較例１〜３について評価結果を表１に示す。 Table 1 shows the evaluation results for Examples 1-2 and Comparative Examples 1-3.
上記、実施例１〜２及び比較例２のシートの０.１〜３.０GＨzでの伝送減衰率の評価結果を図１に示す。
特に、１GHz以上の領域で、実施例１、２は良好な伝送減衰率を示すことが確認された。
The evaluation results of the transmission attenuation factor at 0.1 to 3.0 GHz of the sheets of Examples 1 and 2 and Comparative Example 2 are shown in FIG.
In particular, it was confirmed that Examples 1 and 2 showed good transmission attenuation factors in the region of 1 GHz or more.
実施例３
リグニンスルホン酸ナトリウム（サンエキスＰ２５２；日本製紙ケミカル社製）の１.２％水溶液を調整し、その中に、ＣＮＴ：ＶＧＣＦ−Ｘ（昭和電工製）を加え、ＣＮＴの２.０％液とした。このＣＮＴの２.０％溶液を超音波ホモジナイザー（ＵＳ−６００ＦＣＡＴ；日本精機製）で９０ｍｉｎ処理し（振幅４０μm）、ＣＮＴ分散液を得た。セルロース繊維として、叩解度４８７ｍｌＬＢＫＰ（ＥＣＦパルプ）を４.０％懸濁液とし、この懸濁液に、該ＣＮＴ分散液を該ＬＢＫＰ：１００重量部に対して、ＣＮＴが１０重量部となるように加えた。更に、ポリビニルアミン（カチオファストＶＦＨ；ＢＡＳＦ社製）を１.０重量部加え、硫酸バンド６重量部を加えた後、アルミン酸ナトリウムを加えて、ｐＨ７.３のスラリーを調成した。
この、スラリーを水で０.５％に希釈した後、アニオン性アクリルアミド系凝集剤（ＦＡ−２３０；ハイモ社製）を０.０３重量部添加し、速やかに角型手抄きにて手抄きを行い、米坪９０.１ｇ/ｍ２，厚さ０.１３２ｍｍのシートを得た。
Example 3
A 1.2% aqueous solution of sodium lignin sulfonate (Sun Extract P252; manufactured by Nippon Paper Chemicals Co., Ltd.) was prepared, and CNT: VGCF-X (manufactured by Showa Denko) was added to it, and a 2.0% solution of CNT and did. This CNT 2.0% solution was treated with an ultrasonic homogenizer (US-600FCAT; manufactured by Nippon Seiki Co., Ltd.) for 90 min (amplitude 40 μm) to obtain a CNT dispersion. As a cellulose fiber, a beating degree of 487 ml LBKP (ECF pulp) is made into a 4.0% suspension, and the CNT dispersion is added to this suspension so that the amount of CNT becomes 10 parts by weight with respect to 100 parts by weight of LBKP. Added to. Further, 1.0 part by weight of polyvinylamine (Cathiofast VFH; manufactured by BASF) was added, 6 parts by weight of sulfuric acid band was added, and then sodium aluminate was added to prepare a slurry having a pH of 7.3.
After the slurry was diluted to 0.5% with water, 0.03 part by weight of an anionic acrylamide-based flocculant (FA-230; manufactured by Hymo Co., Ltd.) was added, and the paper was quickly hand-drawn by square hand-drawing. To obtain a sheet having a weight of 90.1 g / m 2 and a thickness of 0.132 mm.
実施例４
調整するリグニンスルホン酸ナトリウムの水溶液を３.０％にしたこと以外は実施例３と同様に実施し、米坪８８.８g/ｍ２，厚さ０.１３０ｍｍのシートを得た。
Example 4
The same procedure as in Example 3 was conducted, except that the aqueous sodium lignin sulfonate solution to be adjusted was 3.0%, to obtain a sheet having a weight of 88.8 g / m 2 and a thickness of 0.130 mm.
比較例４
調整するリグニンスルホン酸ナトリウムの水溶液を４.０％としたこと以外は実施例３と同様に実施し、米坪９１.２g/ｍ２，厚さ０.１３８ｍｍのシートを得た。湿潤強度が不十分であり、体積抵抗値が高かった。
Comparative Example 4
The same procedure as in Example 3 was conducted, except that the aqueous sodium lignin sulfonate solution to be adjusted was 4.0%, to obtain a sheet having a basis weight of 91.2 g / m 2 and a thickness of 0.138 mm. The wet strength was insufficient and the volume resistance value was high.
実施例５
ポリビニルアミンの添加量を０.５重量部としたこと以外は、実施例３と同様に実施し、米坪９２.７g/ｍ２，厚さ０.１２５ｍｍのシートを得た。
Example 5
Except that the addition amount of polyvinylamine was 0.5 parts by weight, the same procedure as in Example 3 was performed to obtain a sheet having a basis weight of 92.7 g / m 2 and a thickness of 0.125 mm.
実施例６
ポリビニルアミンの添加量を２.０重量部としたこと以外は、実施例３と同様に実施し、米坪９１.２g/ｍ２，厚さ０.１３２ｍｍのシートを得た。
Example 6
Except that the addition amount of polyvinylamine was 2.0 parts by weight, the same procedure as in Example 3 was performed to obtain a sheet having a basis weight of 91.2 g / m 2 and a thickness of 0.132 mm.
実施例７
ポリビニルアミンの添加量を３.０重量部としたこと以外は、実施例３と同様に実施し、米坪９２.０g/ｍ２，厚さ０.１３５ｍｍのシートを得た。
Example 7
The same procedure as in Example 3 was conducted, except that the addition amount of polyvinylamine was changed to 3.0 parts by weight, and a sheet having a basis weight of 92.0 g / m 2 and a thickness of 0.135 mm was obtained.
上記の実施例３〜７、比較例４について評価結果を表２に示す。
上記、実施例３〜７及び比較例４のシートの０.１〜３.０GＨzでの伝送減衰率の評価結果を図２に示す。
特に、１GHz以上の領域で、実施例３〜７は良好な伝送減衰率を示すことが確認された。
FIG. 2 shows the evaluation results of the transmission attenuation factor at 0.1 to 3.0 GHz of the sheets of Examples 3 to 7 and Comparative Example 4 described above.
In particular, it was confirmed that Examples 3 to 7 showed good transmission attenuation factors in the region of 1 GHz or more.
本発明による電磁波抑制シートは特に１ＧＨz以上で電磁波吸収性能が十分あり、かつ軽量であるのでコンピューター、携帯電話等の通信機器や電子機器に適用できる。
The electromagnetic wave suppression sheet according to the present invention is particularly applicable to communication devices and electronic devices such as computers and mobile phones because it has a sufficient electromagnetic wave absorption performance at 1 GHz or more and is lightweight.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011034312A JP5571014B2 (en) | 2011-02-21 | 2011-02-21 | Electromagnetic wave suppression sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011034312A JP5571014B2 (en) | 2011-02-21 | 2011-02-21 | Electromagnetic wave suppression sheet |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2012174834A true JP2012174834A (en) | 2012-09-10 |
| JP2012174834A5 JP2012174834A5 (en) | 2013-02-14 |
| JP5571014B2 JP5571014B2 (en) | 2014-08-13 |
Family
ID=46977481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2011034312A Active JP5571014B2 (en) | 2011-02-21 | 2011-02-21 | Electromagnetic wave suppression sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5571014B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110144762A (en) * | 2019-05-30 | 2019-08-20 | 方成 | A kind of preparation method of cellulose extrusion coating paper |
| US11839069B2 (en) | 2018-09-28 | 2023-12-05 | Zeon Corporation | Electromagnetic wave absorbing sheet and method of manufacturing the same |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001081686A (en) * | 1999-09-14 | 2001-03-27 | Oji Paper Co Ltd | Cellulose fiber sheet and molded body |
| JP2005260214A (en) * | 2004-02-12 | 2005-09-22 | Toray Ind Inc | Electromagnetic wave shield material, stereo structure, electromagnetic wave shield property interior material, and image display device |
| JP2006124843A (en) * | 2004-10-26 | 2006-05-18 | Konica Minolta Holdings Inc | Inkjet printing method |
| JP2006152454A (en) * | 2004-11-25 | 2006-06-15 | Konica Minolta Holdings Inc | Pretreating liquid for inkjet printing and inkjet printing method using the same |
| WO2008069287A1 (en) * | 2006-11-30 | 2008-06-12 | Dynax Corporation | Method for production of paper containing carbon nanotube, and paper produced by the method |
| JP2009530504A (en) * | 2006-03-16 | 2009-08-27 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing paper, board and cardboard with high dry strength |
| JP2010040730A (en) * | 2008-08-05 | 2010-02-18 | Tokushu Paper Mfg Co Ltd | Sheet-like article |
| JP2011503271A (en) * | 2007-11-05 | 2011-01-27 | ビーエーエスエフ ソシエタス・ヨーロピア | Glyoxalated N-vinylamine |
-
2011
- 2011-02-21 JP JP2011034312A patent/JP5571014B2/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001081686A (en) * | 1999-09-14 | 2001-03-27 | Oji Paper Co Ltd | Cellulose fiber sheet and molded body |
| JP2005260214A (en) * | 2004-02-12 | 2005-09-22 | Toray Ind Inc | Electromagnetic wave shield material, stereo structure, electromagnetic wave shield property interior material, and image display device |
| JP2006124843A (en) * | 2004-10-26 | 2006-05-18 | Konica Minolta Holdings Inc | Inkjet printing method |
| JP2006152454A (en) * | 2004-11-25 | 2006-06-15 | Konica Minolta Holdings Inc | Pretreating liquid for inkjet printing and inkjet printing method using the same |
| JP2009530504A (en) * | 2006-03-16 | 2009-08-27 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing paper, board and cardboard with high dry strength |
| WO2008069287A1 (en) * | 2006-11-30 | 2008-06-12 | Dynax Corporation | Method for production of paper containing carbon nanotube, and paper produced by the method |
| JP2011503271A (en) * | 2007-11-05 | 2011-01-27 | ビーエーエスエフ ソシエタス・ヨーロピア | Glyoxalated N-vinylamine |
| JP2010040730A (en) * | 2008-08-05 | 2010-02-18 | Tokushu Paper Mfg Co Ltd | Sheet-like article |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11839069B2 (en) | 2018-09-28 | 2023-12-05 | Zeon Corporation | Electromagnetic wave absorbing sheet and method of manufacturing the same |
| CN110144762A (en) * | 2019-05-30 | 2019-08-20 | 方成 | A kind of preparation method of cellulose extrusion coating paper |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5571014B2 (en) | 2014-08-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6620739B2 (en) | Paper or paperboard manufacturing method | |
| González et al. | Effect of the combination of biobeating and NFC on the physico-mechanical properties of paper | |
| JP5528760B2 (en) | Paper made by adding cellulose nanofibers and method for producing the same | |
| JP5420416B2 (en) | Sheet-like material and manufacturing method thereof | |
| JP2016166444A (en) | Paper making method of paper and paper board | |
| JP5416531B2 (en) | Filler pretreatment method and paper containing pretreated filler | |
| Ämmälä et al. | Effect of tempo and periodate-chlorite oxidized nanofibrils on ground calcium carbonate flocculation and retention in sheet forming and on the physical properties of sheets | |
| JP5571014B2 (en) | Electromagnetic wave suppression sheet | |
| JP2020007698A (en) | Inorganic fiber paper | |
| Petroudy et al. | Sugarcane bagasse paper reinforced by cellulose nanofiber (CNF) and bleached softwood kraft (BSWK) pulp | |
| JP2010528196A (en) | Method for producing cellulosic products | |
| JP5317261B2 (en) | Sheet | |
| Ni et al. | Characteristics of high yield pulp and its effect on some typical wet-end issues | |
| AU2019244030B2 (en) | Paper comprising microfibrillated cellulose fibers | |
| Zhao et al. | Effect of saturation adsorption of paper strength additives on the performance of paper | |
| Jo et al. | Development of membrane filter for water treatment using anionic and cationic cellulose nanofibers | |
| JPWO2017002863A1 (en) | Flame retardant paper for radio wave absorber members | |
| JP7238768B2 (en) | flame retardant paper | |
| JP6706523B2 (en) | Electrical insulating paper | |
| JP6255683B2 (en) | Base paper for wallpaper | |
| JP2012174834A5 (en) | ||
| JP6264735B2 (en) | Adhesive tape base paper | |
| Nunes et al. | Cellulose nanofibrills in papermaking—Filler retention, wet web resistance and printability | |
| JP2020023759A (en) | Flame-retardant paper | |
| Korhonen | Flocculation/deflocculation of cellulosic materials and mineral particles by polyelectrolyte complexes and nanocelluloses |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120806 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20121226 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20121226 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20131022 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20131029 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140520 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140523 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140624 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140625 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5571014 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |