JPH0411498B2 - - Google Patents
Info
- Publication number
- JPH0411498B2 JPH0411498B2 JP2769184A JP2769184A JPH0411498B2 JP H0411498 B2 JPH0411498 B2 JP H0411498B2 JP 2769184 A JP2769184 A JP 2769184A JP 2769184 A JP2769184 A JP 2769184A JP H0411498 B2 JPH0411498 B2 JP H0411498B2
- Authority
- JP
- Japan
- Prior art keywords
- sheet
- inorganic
- mfc
- sheets
- fine particles
- 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.)
- Expired
Links
- 238000005266 casting Methods 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 239000010419 fine particle Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000001913 cellulose Substances 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 3
- 239000012784 inorganic fiber Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 description 16
- 239000011230 binding agent Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 6
- 229910010272 inorganic material Inorganic materials 0.000 description 5
- 239000011147 inorganic material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 229920003169 water-soluble polymer Polymers 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
Landscapes
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
- Paper (AREA)
Description
【発明の詳細な説明】
本発明は、ミクロフイブリル化セルロースをバ
インダーとした流延法による無機質微粒子または
無機質短繊維のシート材の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a sheet material of inorganic fine particles or inorganic short fibers by a casting method using microfibrillated cellulose as a binder.
シリカ、アルミナ、酸化チタン、チタン酸カリ
などの無機質粒子または無機質繊維は、一般に、
それらの素材が不燃性、耐熱性、耐薬品性、高剛
性率であるなどの特徴があり、シート状に成形し
たものは種々の用途が考えられる。 Inorganic particles or fibers such as silica, alumina, titanium oxide, and potassium titanate are generally
These materials have characteristics such as being nonflammable, heat resistant, chemical resistant, and have high rigidity, and when molded into sheets, they can be used for a variety of purposes.
これらの無機質でそのサイズが小さいもの、即
ち、微粒子や短繊維をシート状に成形する方法と
しては、抄紙法、流延法、押出成形法などがあ
る。抄紙法は一般に生産性の高い方法であるが、
特に粒子や繊維のサイズが微小であり、また表面
が平滑な場合、100%の歩留りでシートとして取
得することは困難である。また、押出法は多量の
熱可塑性物質の介在が必要であり、無機質含有が
高いシートは製造困難である。これらに対し、流
延法は無機質の歩留りが100%で、かつ無機質含
有率の高いシートが得られる。この方法はまた、
薄い均一なシート(フイルム)の成形に適してい
る。 Methods for forming these small-sized inorganic materials, ie, fine particles and short fibers, into sheet shapes include paper-making methods, casting methods, and extrusion methods. The paper making method is generally a highly productive method, but
In particular, if the particles or fibers are small in size and have a smooth surface, it is difficult to obtain a sheet with a 100% yield. Furthermore, the extrusion method requires the intervention of a large amount of thermoplastic material, making it difficult to produce sheets with a high inorganic content. On the other hand, the casting method has a 100% inorganic yield and produces a sheet with a high inorganic content. This method also
Suitable for forming thin uniform sheets (films).
無機質微粒子や短繊維を流延法でシート化する
には、通常、フイルム形成能力のある物質、例え
ばカルボキシメチルセルロースやポリビニルアル
コールなどの水溶性高分子の水溶液と無機質を混
合してスラリーとし、水平基盤上に流延し、乾燥
してシート化する。即ち、水溶性高分子をバイン
ダーとしたシートである。このようにして製造し
たシートは、無機質自体が多孔室でない限り、全
体に緻密構造にすぎて含浸用には不適当である。
また、一般にシートが吸湿性を有するようになり
用途によつては問題になる。 In order to form inorganic fine particles or short fibers into a sheet by the casting method, the inorganic material is usually mixed with an aqueous solution of a water-soluble polymer such as carboxymethyl cellulose or polyvinyl alcohol to form a slurry, and then the inorganic material is made into a slurry. It is cast on top, dried and made into a sheet. That is, it is a sheet using a water-soluble polymer as a binder. The sheets produced in this way have too dense a structure as a whole and are unsuitable for impregnation, unless the inorganic material itself is porous.
Additionally, the sheet generally becomes hygroscopic, which can be a problem depending on the application.
さらに、水溶性高分子によつては乾燥時の収縮
が大きく、部分的な内部応力、例えば周辺部と中
央部で差ができ、変形や割れの起りやすいシート
になる。水以外の物質、例えば有機溶剤を使用す
ることについては、一般に無機質は有機溶剤に対
するなじみが悪く、スラリー中での分散性が悪く
なるので良好なシートが得られ難く、また、コス
トが高くなる。 Furthermore, some water-soluble polymers have large shrinkage during drying, resulting in partial internal stress, such as a difference between the periphery and the center, resulting in sheets that are prone to deformation and cracking. Regarding the use of substances other than water, such as organic solvents, inorganic substances generally have poor compatibility with organic solvents and have poor dispersibility in slurry, making it difficult to obtain good sheets and increasing costs.
発明者等はさきに、ミクロフイブリル化セルロ
ース(以下MFCと略す)が、無機質粒子の抄紙
法を用いたシート化の際のバインダー兼分散剤と
してすぐれたものであることを見出し、特許出願
したが、今回このMFCが、流延法におけるバイ
ンダーとしても有用であることを見出した。 The inventors previously discovered that microfibrillated cellulose (hereinafter abbreviated as MFC) is an excellent binder and dispersant when forming sheets using inorganic particle papermaking methods, and filed a patent application. However, we have now discovered that this MFC is also useful as a binder in the casting method.
即ち、本発明は無機質微粒子または無機質短繊
維と、MFCを必須成分として含有する水性スラ
リーを平面基盤上に流延し、乾燥することを特徴
とする無機質シート材の製造法に関するものであ
る。 That is, the present invention relates to a method for producing an inorganic sheet material, which comprises casting an aqueous slurry containing inorganic fine particles or inorganic short fibers and MFC as essential components onto a flat substrate and drying the slurry.
本発明に使用するMFCとは、バルブやリンタ
ーなどのセルロース原料を特開昭56−100801号明
細書に開示された方法を用いて、水中で粘状叩解
して得られるもので、同明細書には「微小繊維状
セルロース」として定義されている。MFCは、
セルロース繊維が微細に分割され、径が数μm以
下の多数のフイブリルの集合体となつているもの
である。フイブリルの長さは、原料や製造条件に
よつて多少異るが、木材パルプから得られたもの
は数百μm程度のものである。MFCは原料の6
倍程度以上の保水性があり、水中でセルロース固
形分0.4%以上の濃度で分散したものは、安定な
懸濁液を形成する。この懸濁液を流延して乾燥す
ると半透明のフイルムが得られる。 The MFC used in the present invention is obtained by beating cellulose raw materials such as bulbs and linters into a viscous state in water using the method disclosed in JP-A-56-100801. It is defined as "microfibrous cellulose". MFC is
Cellulose fibers are finely divided into aggregates of many fibrils with diameters of several μm or less. The length of fibrils varies somewhat depending on the raw material and manufacturing conditions, but those obtained from wood pulp are on the order of several hundred μm. MFC is raw material 6
It has a water retention capacity of about twice as much, and when dispersed in water at a concentration of cellulose solid content of 0.4% or more, it forms a stable suspension. When this suspension is cast and dried, a translucent film is obtained.
本発明に適用する無機質微粒子または無機質短
繊維とは、アルミニウム、マグネシウム、鉄、チ
タン、ニツケルなどの酸化物、水酸化物、硫化
物、塩化物または遊離金属などや、炭化珪素、炭
化チタン、窒化珪素、チタン酸カリ、雲母、バー
ミキユライト、ロツクウール、ガラスフアイバ
ー、シラスバルーンなどであり、形態的には針
状、繊維状、柱状、板状、球状、無定形などのも
のを包含する。 The inorganic fine particles or inorganic short fibers used in the present invention include oxides, hydroxides, sulfides, chlorides, or free metals such as aluminum, magnesium, iron, titanium, and nickel, as well as silicon carbide, titanium carbide, and nitride. These include silicon, potassium titanate, mica, vermiculite, rock wool, glass fiber, and shirasu balloon, and include needle-like, fibrous, columnar, plate-like, spherical, and amorphous shapes.
上記の無機質とMFCの水懸濁液を混合し、水
平基盤上に流延し、乾燥すると、自己形状保持性
のあるシートが得られる。MFCは、その固形分
の5倍量程度までの無機質のバインダーとしてシ
ート化させることができる。従つて、有機質含量
の少い焼成用シートの製造に適している。MFC
をバインダーとして用いた場合、乾燥時の収縮が
少く、含浸性、加工性に富むシートが得られる。 When an aqueous suspension of the above inorganic material and MFC is mixed, cast on a horizontal substrate, and dried, a sheet with self-shape retention is obtained. MFC can be formed into a sheet as an inorganic binder with an amount of up to five times its solid content. Therefore, it is suitable for producing sheets for baking with a low organic content. MFC
When used as a binder, a sheet with little shrinkage during drying and excellent impregnability and processability can be obtained.
無機質微粒子とMFCを含むスラリーに、他種
のバインダーを加え、シート強度を向上させるこ
とも可能である。MFCは、特に水溶性高分子と
の親和性が良好であり、水溶性高分子を第2のバ
インダーとして併用することにより、種々の密度
のシートを製造することができる。 It is also possible to improve sheet strength by adding other types of binders to the slurry containing inorganic fine particles and MFC. MFC has particularly good affinity with water-soluble polymers, and by using water-soluble polymers together as a second binder, sheets of various densities can be manufactured.
本発明の方法によつて得たシート材は、含浸用
基材、ラミネート用基材、焼成用シトなどとして
使用することができ、セパレーター、スピーカー
振動板、プリント基板、コンデンサー、面発熱
体、その他の製造に利用することができる。 The sheet material obtained by the method of the present invention can be used as a base material for impregnation, a base material for lamination, a sheet for firing, etc., and can be used as a separator, a speaker diaphragm, a printed circuit board, a capacitor, a surface heating element, etc. It can be used for manufacturing.
以下に実施例をあげて本発明を説明する。 The present invention will be explained below with reference to Examples.
実施例 1
固形分濃度2%のMFC懸濁液100重量部に、平
均粒径1.0μmの水酸化アルミニウム
(Al2O3.3H2O 住友化学製C−301)2重量部を
加えて混合撹拌し、水性スラリーを得た。このも
のを平面上におかれたポリエステルシート上に、
クリアランス1mmのアプリケーターを用いて流延
し、自然乾燥して厚み36μmの均一なシートを得
た。乾燥工程における平面方向の収縮率は0%で
あつた。Example 1 2 parts by weight of aluminum hydroxide (Al 2 O 3 .3H 2 O C-301 manufactured by Sumitomo Chemical) with an average particle size of 1.0 μm was added to 100 parts by weight of MFC suspension with a solid content concentration of 2% and mixed. Stirring resulted in an aqueous slurry. Place this on a polyester sheet placed on a flat surface.
It was cast using an applicator with a clearance of 1 mm and air-dried to obtain a uniform sheet with a thickness of 36 μm. The shrinkage rate in the plane direction during the drying process was 0%.
上記シートを1300℃の電気炉中で3時間焼成し
て自己形状保持性のあるアルミナシートを作成し
た。焼成前後の平面方向の収縮率は約14%であつ
た。 The above sheet was fired in an electric furnace at 1300°C for 3 hours to produce an alumina sheet with self-shape retention. The shrinkage rate in the planar direction before and after firing was approximately 14%.
比較例 1
実施例1のMFC懸濁液にかえて、固形分濃度
2%のカルボキシメチルセルロース水溶液を用い
たほかは実施例1と同様にして、流延法によりシ
ートを得た。Comparative Example 1 A sheet was obtained by the casting method in the same manner as in Example 1, except that an aqueous carboxymethyl cellulose solution with a solid content concentration of 2% was used in place of the MFC suspension in Example 1.
乾燥工程における収縮率は、流延方向が約4
%、流延方向と直角の方向に約7%であつた。乾
燥シートの厚みは約22μmであつたが、各所にひ
び割れを生じていた。ひび割れのない部分をと
り、1300℃で3時間焼成し、アルミナシートを得
た。焼成前後の収縮率は34%であつた。 The shrinkage rate in the drying process is approximately 4 in the casting direction.
%, and about 7% in the direction perpendicular to the casting direction. The thickness of the dried sheet was approximately 22 μm, but cracks had appeared in various places. A part without cracks was taken and fired at 1300°C for 3 hours to obtain an alumina sheet. The shrinkage rate before and after firing was 34%.
比較例 2
実施例1のMFC懸濁液にかえて、固形分濃度
2%のポリビニルアルコール水溶液を用いたほか
は、実施例1と同様にして、流延法によりシート
を得た。乾燥シートの厚みは27μmであつた。同
様に1300℃で焼成し、アルミナシートを得た。乾
燥工程の収縮率は0%、焼成工程の収縮率は25%
であつた。Comparative Example 2 A sheet was obtained by the casting method in the same manner as in Example 1, except that an aqueous polyvinyl alcohol solution having a solid content concentration of 2% was used in place of the MFC suspension in Example 1. The thickness of the dry sheet was 27 μm. Similarly, it was fired at 1300°C to obtain an alumina sheet. The shrinkage rate in the drying process is 0%, and the shrinkage rate in the baking process is 25%.
It was hot.
Claims (1)
イブリル化セルロースを必須成分とする水性スラ
リーを平面基盤上に流延し、乾燥することを特徴
とする無機質シート材の製造法。1. A method for producing an inorganic sheet material, which comprises casting an aqueous slurry containing inorganic fine particles or short inorganic fibers and microfibrillated cellulose as essential components onto a flat substrate and drying the slurry.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2769184A JPS60171262A (en) | 1984-02-16 | 1984-02-16 | Manufacture of inorganic sheet material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2769184A JPS60171262A (en) | 1984-02-16 | 1984-02-16 | Manufacture of inorganic sheet material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60171262A JPS60171262A (en) | 1985-09-04 |
JPH0411498B2 true JPH0411498B2 (en) | 1992-02-28 |
Family
ID=12227988
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2769184A Granted JPS60171262A (en) | 1984-02-16 | 1984-02-16 | Manufacture of inorganic sheet material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60171262A (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE8533598U1 (en) * | 1985-11-29 | 1987-04-02 | Thiel, Bernhard, 6653 Blieskastel | Membrane for electro-acoustic transducers |
DE19628324A1 (en) * | 1996-07-13 | 1998-01-15 | Hocepro Gmbh I G | Cellulose fibrils |
FR2774702B1 (en) * | 1998-02-11 | 2000-03-31 | Rhodia Chimie Sa | ASSOCIATION BASED ON MICROFIBRILLES AND MINERAL PARTICLES PREPARATION AND USES |
KR20060134152A (en) * | 2004-04-15 | 2006-12-27 | 엔.브이. 베카에르트 에스.에이. | Method for Making Unsintered Metal Fiber Media |
JP5113685B2 (en) * | 2008-09-09 | 2013-01-09 | 三菱製紙株式会社 | Electrochemical element separator |
-
1984
- 1984-02-16 JP JP2769184A patent/JPS60171262A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS60171262A (en) | 1985-09-04 |
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