JPH08302059A - Inorganic lightweight molding - Google Patents

Inorganic lightweight molding

Info

Publication number
JPH08302059A
JPH08302059A JP10754895A JP10754895A JPH08302059A JP H08302059 A JPH08302059 A JP H08302059A JP 10754895 A JP10754895 A JP 10754895A JP 10754895 A JP10754895 A JP 10754895A JP H08302059 A JPH08302059 A JP H08302059A
Authority
JP
Japan
Prior art keywords
inorganic
weight
water
compound
polymer compound
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
Application number
JP10754895A
Other languages
Japanese (ja)
Other versions
JP3561728B2 (en
Inventor
Takuji Hayashi
卓次 林
Yasuhei Takeuchi
泰平 竹内
Saburo Imoto
三郎 井本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TSUYATSUKU KK
Original Assignee
TSUYATSUKU KK
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Filing date
Publication date
Application filed by TSUYATSUKU KK filed Critical TSUYATSUKU KK
Priority to JP10754895A priority Critical patent/JP3561728B2/en
Publication of JPH08302059A publication Critical patent/JPH08302059A/en
Application granted granted Critical
Publication of JP3561728B2 publication Critical patent/JP3561728B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Abstract

PURPOSE: To obtain a lightweight molding having flexibility by using a cement, a wood chip cement, slate waste powder, etc., and an inorganic compound such as silas balloon, etc., as raw materials. CONSTITUTION: This inorganic lightweight molding comprises a composition consisting of an inorganic compound, a water-soluble polymer compound having 10-300MPa tensile strength of a coating film, 30-65mN/m surface tension in 0.4wt.% aqueous solution at 20 deg.C and containing two or more hydroxy groups in one molecule, a water-soluble polymer compound containing one or more carboxyl groups or sulfone groups in one molecule and/or an anionic surfactant and a polymer compound having 0.1-10MPa tensile strength of a coating film, 200-2,000% elongation at break, -40 to 30 deg.C second-order transition temperature and 30-200cal/cc cohesive energy, contains >=50wt.% of the inorganic compound and has <=0.4g/cm<3> apparent density.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、炭酸カルシウム、硫酸
バリウムなどのような水不溶性の炭酸塩、硫酸塩、リン
酸塩、セメント、マグネシア、ジルコニア、フェライト
などの水不溶性の酸化物、滑石、ジャモン岩などの岩
石、カオリン、モンモリロナイト、パイロフィライトの
ような粘土鉱物などあらゆる形状の無機化合物を主体と
する、連続気泡を有する無機質系軽量成形物に関するも
のである。
The present invention relates to water-insoluble carbonates such as calcium carbonate and barium sulfate, sulfates, phosphates, cements, water-insoluble oxides such as magnesia, zirconia and ferrite, talc, The present invention relates to an inorganic light-weight molded product having open cells, which is mainly composed of rocks such as jammon rock, clay minerals such as kaolin, montmorillonite, and pyrophyllite, and which has open cells.

【0002】[0002]

【従来の技術】本発明において使用する無機化合物は、
いずれも比重2乃至6であり、その成形物は重く、脆
く、とくに曲げに弱い。したがって、有機または無機の
繊維状物をブレンドし木片セメント、スレートなどとし
て商品化されているが、重いという欠点はそのままであ
る。
Inorganic compounds used in the present invention are:
Each of them has a specific gravity of 2 to 6, and the molded product is heavy, brittle, and particularly weak in bending. Therefore, although it is commercialized as a wood chip cement, a slate, etc. by blending an organic or inorganic fibrous material, the drawback of being heavy remains.

【0003】また、これら無機化合物の成形物の特徴は
耐熱性、不燃性にあるので、これらの特徴を保持して軽
量化と柔軟性を付与することは困難な問題で、これを解
決した商品はまだ現れていない。
Further, since the features of the molded products of these inorganic compounds are heat resistance and nonflammability, it is difficult to keep these features and provide weight reduction and flexibility. Has not appeared yet.

【0004】[0004]

【発明が解決しようとする課題】本発明は、繊維状に限
定することなくあらゆる形状、すなわち粉状、粒状、針
状、鱗片状など絡み合うことのない形状の無機化合物を
も原料として、軽量かつ柔軟性を有する成形物を得る目
的で無機化合物に加えるべき各種化合物やその配合比に
ついて検討を加えたものである。
DISCLOSURE OF THE INVENTION The present invention is not limited to fibrous materials, and can be used as a raw material for an inorganic compound of any shape, that is, powdery, granular, acicular, scale-like, etc., which is not entangled, and is lightweight and lightweight. Various compounds to be added to the inorganic compound for the purpose of obtaining a molded article having flexibility and the compounding ratio thereof are examined.

【0005】先に本発明者は、特願平6−221475号にお
いて、リグノセルロースの含有量50重量%以上の連続気
泡構造をもった軽量成形物が得られることを見出した。
同様な方法で気泡構造によって軽量化を試みたが、無機
化合物の含有量50重量%以上では見掛け密度0.4g/cm3
以下の均一な気泡構造が得られず、目的とする成形物が
得られなかった。
The present inventor has previously found in Japanese Patent Application No. 6-221475 that a lightweight molded product having an open cell structure with a lignocellulose content of 50% by weight or more can be obtained.
In the same way, we tried to reduce the weight by using a cell structure, but when the content of inorganic compounds was 50% by weight or more, the apparent density was 0.4 g / cm 3
The following uniform cell structure could not be obtained, and the target molded product could not be obtained.

【0006】例えば、セメント粉末(比重3.15)を用い
て、セメントの含有量がそれぞれ54重量%、60重量%、
70重量%では見掛け密度0.4g/cm3以下では亀裂の入っ
たシートしか得られず、0.45乃至0.5g/cm3の見掛け密
度において初めて綺麗なシートが得られた。またセメン
ト37重量%では、バインダー63重量%の有機ポリマー主
体の組成で気泡構造の均一な見掛け密度0.37g/cm3のシ
ートが得られている。
For example, using cement powder (specific gravity 3.15), the content of cement is 54% by weight, 60% by weight,
At 70% by weight, only a cracked sheet was obtained at an apparent density of 0.4 g / cm 3 or less, and a clean sheet was obtained only at an apparent density of 0.45 to 0.5 g / cm 3 . Also, with 37% by weight of cement, a sheet having a uniform apparent density of 0.37 g / cm 3 with a cell structure was obtained with a composition of 63% by weight of binder and mainly composed of an organic polymer.

【0007】しかしながら、これら無機化合物の成形物
の用途としては、併用する可能性の有機物の使用量も制
限を受けるので、添加するバインダー量を極力少なくす
る必要がある。したがって、無機化合物の含有量50重量
%以上の成形物で見掛け密度0.4/cm3以下のものを得る
ためには、バインダーに頼らない別の方法が必要であ
る。本発明は、以上の点を課題として検討を加えたもの
である。
However, the amount of the binder to be added needs to be reduced as much as possible because the amount of the organic substance that can be used in combination is limited in the use of the molded product of these inorganic compounds. Therefore, in order to obtain a molded product having an inorganic compound content of 50% by weight or more and having an apparent density of 0.4 / cm 3 or less, another method that does not rely on a binder is necessary. The present invention has been studied by taking the above points into consideration.

【0008】[0008]

【課題を解決するための手段】あらゆる形状の無機化合
物の粉粒体を均質な気泡構造を保持しながら、なるべく
少量のバインダーで結合させて成形物を作る場合、乾式
法よりも無機化合物を濡らす水を溶媒とする湿式法の方
が好ましい。その製造に際し、水に可溶性あるいは乳化
している接着剤を用いるので、成形時に加熱し水分を蒸
発させるときこれら接着剤の表面への移行を防止しなけ
ればならない。また、気泡構造を作るには、無機化合物
のスラリー中に空気を吹い込み、そのスラリー中に細か
く分散された気泡を保持したまま乾燥せねばならない
が、その際気泡の合体を防止しなければ均質な気泡構造
は得られない。これらの目的の達成には次の手段が採用
された。
[Means for Solving the Problems] In the case of forming a molded product by binding a powdery or granular material of any shape of an inorganic compound with a binder as small as possible while maintaining a homogeneous cell structure, the inorganic compound is wetted rather than a dry method. A wet method using water as a solvent is preferable. Since an adhesive which is soluble or emulsified in water is used in the production thereof, it is necessary to prevent migration of these adhesives to the surface when heating and evaporating water during molding. Further, in order to form a cell structure, air must be blown into the slurry of the inorganic compound and dried while retaining the finely dispersed cells in the slurry. A fine cell structure cannot be obtained. The following measures were adopted to achieve these objectives.

【0009】すなわち、(1)皮膜の引張強さ10MPa(メガ
パスカル)以上、好ましくは30以上300MPa、かつ20℃に
おける濃度0.4重量%水溶液の表面張力65mN/m(ミリ
ニュートン/メートル)以下30mN/mで、1分子中に水
酸基(以下OH基と略記)2個以上を有する水溶性の高分
子化合物を、無機化合物に対し10重量%以下0.5重量%
の範囲で、(2)1分子中に2個以上のカルボキシル基ま
たはスルホン基を有する水溶性の高分子化合物または/
及びアニオン性界面活性剤を好ましくは、無機化合物に
対し20重量%以下1重量%の範囲で、(3)皮膜の引張強
さ10MPa以下0.1MPa、好ましくは6以下0.5MPaの範
囲、破断伸び率2,000%以下200%、好ましくは1,800%
以下300%の範囲、2次転移温度(以下Tgと略記)30乃
至−40℃、好ましくは10乃至−20℃、かつ凝集エネルギ
ー密度20乃至200(cal/cc)、好ましくは60乃至120(cal/c
c)である高分子化合物を好ましくは無機化合物に対し、
5乃至100重量%の範囲で配合して、水を溶媒としたス
ラリーを作成し、それに撹拌しながら空気を吹き込んだ
のちシート状に成形もしくは型枠内に注入して加熱し水
を蒸発させ成形する。
That is, (1) the tensile strength of the coating is 10 MPa (megapascal) or more, preferably 30 or more and 300 MPa, and the surface tension of a 0.4% by weight aqueous solution at 20 ° C. is 65 mN / m (millinewton / meter) or less 30 mN / m, a water-soluble polymer compound having two or more hydroxyl groups (hereinafter abbreviated as OH groups) in one molecule is 10% by weight or less and 0.5% by weight or less with respect to the inorganic compound.
Within the range of (2) a water-soluble polymer compound having two or more carboxyl groups or sulfone groups in one molecule or /
And an anionic surfactant are preferably in the range of 20% by weight or less and 1% by weight with respect to the inorganic compound, (3) the tensile strength of the film is 10 MPa or less and 0.1 MPa, preferably 6 or less and 0.5 MPa, and the elongation at break. 2,000% or less 200%, preferably 1,800%
In the following range of 300%, second-order transition temperature (hereinafter abbreviated as Tg) 30 to -40 ° C, preferably 10 to -20 ° C, and cohesive energy density 20 to 200 (cal / cc), preferably 60 to 120 (cal / c
c) the polymer compound is preferably an inorganic compound,
Mix in the range of 5 to 100% by weight to make a slurry with water as a solvent, blow air while stirring it, and then mold it into a sheet or inject it into the mold to heat and evaporate the water to mold it. To do.

【0010】(1)の水溶性高分子化合物としては、ポリ
ビニールアルコール(PVAと略記)の誘導体、セルロー
ス誘導体などである。誘導体としては、アルキル基の炭
素数が1乃至8のアルコールあるいはアルデヒドのエー
テル化共重合物、あるいはアセタール化共重合物であ
る。好ましい添加量は無機物化合物に対し1乃至3重量
%であるが、過剰に存在すれば気泡構造の不均一化と成
形不能を起こすので、いかなる無機化合物に対しても10
重量%を越してはならない。
Examples of the water-soluble polymer compound (1) include polyvinyl alcohol (abbreviated as PVA) derivatives and cellulose derivatives. The derivative is an etherification copolymer or an acetalization copolymer of an alcohol or aldehyde having an alkyl group having 1 to 8 carbon atoms. The preferable addition amount is 1 to 3% by weight with respect to the inorganic compound, but if it is present in excess, it causes non-uniform cell structure and unmoldable.
Do not exceed% by weight.

【0011】(2)の1分子中に2個以上のカルボキシル
基またはスルホン基を有する水溶性高分子化合物として
はポリアクリル酸及びその誘導体、ポリメタアクリル酸
及びその誘導体、マレイン酸の共重合物、カルボキシメ
チルセルロース(CMC)、アルギン酸ソーダ、ポリビニ
ルスルホン酸ソーダなどである。アニオン性界面活性剤
としては、脂肪酸ソーダ、高級アルコール硫酸化エステ
ル塩、アルキルベンゼンスルホン酸塩などである。これ
らは気泡を抱き込んだスラリーの流動性を改善し、同時
に加熱成形時の高分子化合物の成形物表面へのマイグレ
イション防止に効果的であることがわかった。そのた
め、加熱成形時の水の蒸発速度を上げることができ、乾
燥時間の短縮が可能となった。この場合も、最適添加量
があり、それぞれ、あるいは両者併用しても無機化合物
の0.5乃至20重量%、好ましくは0.5乃至10重量%であっ
て、20重量%を越えてはならない。それ以上の量が添加
されれば、かえって気泡の構造の不均一とスラリーの流
動性の低下を示す。
As the water-soluble polymer compound having two or more carboxyl groups or sulfone groups in one molecule of (2), polyacrylic acid and its derivative, polymethacrylic acid and its derivative, and a copolymer of maleic acid. , Carboxymethyl cellulose (CMC), sodium alginate, sodium polyvinyl sulfonate, and the like. Examples of anionic surfactants include fatty acid soda, higher alcohol sulfate ester salts, and alkylbenzene sulfonates. It was found that these improve the fluidity of the slurry containing air bubbles and, at the same time, are effective in preventing the migration of the polymer compound onto the surface of the molded product during heat molding. Therefore, the evaporation rate of water during heat molding can be increased, and the drying time can be shortened. In this case, too, there is an optimum addition amount, which is 0.5 to 20% by weight, preferably 0.5 to 10% by weight, and not more than 20% by weight of the inorganic compound, either individually or in combination. On the other hand, if more than that amount is added, the structure of the bubbles becomes non-uniform and the fluidity of the slurry decreases.

【0012】(3)の接着剤となる高分子化合物として
は、例えばブタジエン含有量が35重量%以上のスチレン
−ブタジエン共重合物(SBR),メタアクリル酸メチル
−ブタジエン系共重合物(MBR)、エチレン含有量5乃
至50重量%のエチレン−酢酸ビニル共重合物(EVA
C)、酢酸ビニル含有量80重量%以下の酢酸ビニル−ア
クリル酸エステル共重合物、酢酸ビニル−ビニルエステ
ル共重合物及び酢酸ビニル−ビニルエーテル共重合物な
どである。
As the polymer compound serving as the adhesive of (3), for example, a styrene-butadiene copolymer (SBR) having a butadiene content of 35% by weight or more, a methyl methacrylate-butadiene copolymer (MBR). Ethylene-vinyl acetate copolymer having an ethylene content of 5 to 50% by weight (EVA
C), vinyl acetate-acrylic acid ester copolymers, vinyl acetate-vinyl ester copolymers and vinyl acetate-vinyl ether copolymers having a vinyl acetate content of 80% by weight or less.

【0013】(1)、(2)、(3)の3成分のみを無機化合物
に添加しても見掛け密度0.4g/cm3以下の無機化合物の
含有量50重量%以上の成形物は得られない。いろいろ検
討した結果、成形物中のすべての無機化合物の容積率を
20%以上にすることと、気泡を含有したスラリーを加熱
乾燥して成形する際の下記の式で定義される見掛けの容
積収縮率(S)が30%以下、好ましくは25%以下にすれば
亀裂のない成形物が得られることがわかった。S=0の
場合の成形物の密度をC0、実際に成形された成形物の
密度をC1とすると、その時のSは、下記のとおりであ
る。
Even if only three components (1), (2) and (3) are added to an inorganic compound, a molded product having an apparent density of 0.4 g / cm 3 or less and an inorganic compound content of 50% by weight or more can be obtained. Absent. As a result of various studies, the volume ratio of all inorganic compounds in the molded product was determined.
If it is 20% or more and the apparent volumetric shrinkage rate (S) defined by the following formula when heating and drying the slurry containing bubbles is 30% or less, preferably 25% or less It was found that a crack-free molding was obtained. Assuming that the density of the molded product when S = 0 is C 0 and the density of the actually molded product is C 1 , S at that time is as follows.

【0014】S(%)=(1−C0/C1)×100S (%) = (1-C 0 / C 1 ) × 100

【0015】ここでC0は次式によって算出することが
できる。 C0=(気泡を保持したスラリーの密度)×(空気を吹込む
前のスラリーの固形分率)
Here, C 0 can be calculated by the following equation. C 0 = (density of slurry holding air bubbles) × (solid content of slurry before blowing air)

【0016】この様にして求められるSを30%以下にす
る方法として、粒径5〜1,000μm、好ましくは10〜500
μm、嵩比重0.8以下、好ましくは0.5以下の無機質バル
ーンを、無機化合物と合計した総容積率が成形物中で20
%以上になるような量を添加する。
As a method for reducing the S obtained in this way to 30% or less, the particle size is 5 to 1,000 μm, preferably 10 to 500.
The total volume ratio of inorganic balloons having a particle size of μm and a bulk specific gravity of 0.8 or less, preferably 0.5 or less is 20 in the molded product.
% Or more to be added.

【0017】無機質バルーンとしては、ケイ酸系のシラ
スバルーン、ガラスバルーン、シリカバルーン、フライ
アッシュバルーン、パーライト、バーミキュライトな
ど、非ケイ酸系のアルミナ、ジルコニア、カーボンなど
のバルーンである。
Examples of the inorganic balloons include silicic acid type silas balloons, glass balloons, silica balloons, fly ash balloons, perlite and vermiculite, and non-silicic acid type alumina, zirconia and carbon balloons.

【0018】このようにして、無機質化合物と無機質バ
ルーンによる無機質50重量%以上で見掛け密度0.4g/cm
3以下の均一な連続気泡を有する成形物が得られる。
In this way, the apparent density of the inorganic compound and the inorganic balloon is 50 g or more and the apparent density is 0.4 g / cm.
A molded product having uniform open cells of 3 or less is obtained.

【0019】以上のような少なくとも4つの成分を水中
に添加、よく混合した後、そのスラリー中に空気を吹き
込み泡立てる。スラリーの水分量、粘度は勿論、同一ス
ラリーでも空気吹き込み時の撹拌速度により気泡の大き
さ、分散状態は変化するが、これらの条件を一定にして
おけば、前述の各成分の作用により一定の気泡構造の成
形物を得ることができる。
At least four components as described above are added to water and mixed well, and then air is blown into the slurry to foam. The water content and viscosity of the slurry are, of course, the same slurry, but the size and dispersion state of the bubbles change depending on the stirring speed when air is blown in. However, if these conditions are made constant, the action of each of the above-mentioned components makes it constant. A molded product having a cell structure can be obtained.

【0020】気泡を保持したスラリーは乾燥機で水を蒸
発して成形する。その際に、テフロンシートあるいはテ
フロンで表面加工したシートはあるいはベルト上で、ま
たは離形剤を塗布した金型で乾燥すれば成形物の取り出
しは容易になる。またエンドレスのシート上に連続的に
気泡を有するスラリーを吐出し、乾燥取り出せば連続発
泡主体のシートを得ることができる。またスラリーによ
く濡れる素材のシートやフィルム、例えば紙、織布、不
織布モルタル、ガラス繊維マット、木の板、プラスチッ
ク板またはシート、アルミニウム板、鋼板などの金属
板、アルミニウムなどの金属箔などの上で成形すればリ
グノセルロース発泡体が積層された一体成形も可能であ
る。
The slurry containing air bubbles is molded by evaporating water in a dryer. At that time, if the Teflon sheet or the sheet surface-treated with Teflon is dried on a belt or a mold coated with a release agent, the molded product can be easily taken out. Further, a continuous foaming-based sheet can be obtained by continuously discharging a slurry having bubbles on an endless sheet, and drying and taking out the slurry. Also, on sheets or films of materials that are well wetted by the slurry, such as paper, woven cloth, non-woven mortar, glass fiber mats, wooden boards, plastic boards or sheets, metal boards such as aluminum boards and steel sheets, metal foils such as aluminum. It is also possible to perform integral molding by laminating lignocellulosic foams.

【0021】また、無機質50重量%以上であれば、有機
質繊維状物質(例えば羊毛、綿、麻などの天然繊維、各
種有機合成繊維)、各種形状のリグノセルロース(繊維
状、棒状、粉状、鱗片状など)を混合しても差支えな
い。
Further, if the content of the inorganic substance is 50% by weight or more, organic fibrous substances (for example, natural fibers such as wool, cotton and hemp, various organic synthetic fibers), and various shapes of lignocellulose (fibrous, rod-like, powdery, (Scaly, etc.) can be mixed.

【0022】上記無機質軽量成形物の成分中にさらに、
OH基またはカルボキシル基と反応し化学結合し得る官
能基を1分子中に2個以上有する化合物を成形物組成中
の有機分の0.5〜2.0重量%含有させるとよい。このよう
な有機化合物としては、例えばグリオキザール、トリメ
チロールメラミン、トリス(2−ヒドロキシエチル)−イ
ソシアヌレイトなどである。
In addition to the above components of the inorganic lightweight molded article,
A compound having two or more functional groups capable of chemically bonding with an OH group or a carboxyl group in one molecule may be contained in an amount of 0.5 to 2.0% by weight of the organic content in the composition of the molded product. Examples of such organic compounds include glyoxal, trimethylolmelamine, and tris (2-hydroxyethyl) -isocyanurate.

【0023】さらに本発明の成形物の表面をフッ素樹脂
などにより撥水加工すると防水性も付与することができ
るし、他に必要に応じて種々の添加剤、例えば芳香剤、
防カビ剤、防菌剤、着色剤などを適宜成形物の性質を損
なわない範囲で添加することができる。
Further, if the surface of the molded article of the present invention is treated to be water-repellent with a fluororesin or the like, waterproofness can be imparted, and if necessary, various additives such as aromatic agents,
Antifungal agents, antibacterial agents, coloring agents and the like can be added appropriately within a range that does not impair the properties of the molded product.

【0024】[0024]

【作用】無機化合物、例えばポルトランドセメント粉末
は後述する無機中空体のバルーンと共に成形物の骨格を
形成する。無機中空体のバルーンは成形物の軽量化に貢
献し、気泡を連行した有機結合剤の乾燥皮膜と共に軽量
成形物の機械的性質の向上に寄与する。
The inorganic compound, for example, Portland cement powder, forms the skeleton of the molded product together with the inorganic hollow balloon described later. The balloon of the inorganic hollow body contributes to the weight reduction of the molded product, and contributes to the improvement of the mechanical properties of the lightweight molded product together with the dry film of the organic binder entraining air bubbles.

【0025】分子中にOH基を有する例えばPVAのよ
うな水溶性高分子化合物は、10重量%以下〜0.5重量%
の範囲内での添加で発泡過程における気泡の安定化と機
械的強度の増大に寄与する。そのためには皮膜の引張強
さは少なくとも10MPa以上であることが必要であり、気
泡を安定化するためには、高分子化合物の0.4重量%水
溶液の表面張力は水よりも小さい65mN/m以下で小さ
ければ小さいほどよい結果が得られるが、30℃以上の水
中で水溶性高分子が析出するものは気泡安定性が失われ
る。
The water-soluble polymer compound having an OH group in the molecule, such as PVA, is 10% by weight or less to 0.5% by weight.
Addition within the range contributes to stabilization of bubbles in the foaming process and an increase in mechanical strength. For that purpose, the tensile strength of the film must be at least 10 MPa or more, and in order to stabilize the bubbles, the surface tension of a 0.4 wt% aqueous solution of the polymer compound is 65 mN / m or less, which is smaller than that of water. The smaller the value, the better the results obtained, but the water-soluble polymer that precipitates in water at 30 ° C or higher loses bubble stability.

【0026】高分子成分として、これら接着剤としての
高分子と気泡の安定化剤としての高分子成分のほかに、
成形前の流動性を調節、改善し、接着剤や気泡の安定化
剤のマイグレイションを防止する作用をするのが、水溶
性高分子であって分子中にCOOH基2個以上を有する
もの、例えばポリアクリル酸、CMCなどである。ま
た、アニオン性界面活性剤も同様に作用し、かつ、ポリ
アクリル酸等の高分子と混合しても、流動性改善やマイ
グレイション防止に役立つ。
As the polymer component, in addition to the polymer as the adhesive and the polymer component as the bubble stabilizer,
It is a water-soluble polymer having two or more COOH groups in the molecule, which functions to control and improve the fluidity before molding and prevent migration of the adhesive or bubble stabilizer. For example, polyacrylic acid, CMC and the like. Further, the anionic surfactant acts similarly, and when mixed with a polymer such as polyacrylic acid, it is useful for improving fluidity and preventing migration.

【0027】本発明の無機質系軽量成形物は、上述の無
機化合物と無機質バルーン、特定の3種の水溶性高分子
化合物から構成するもので、更に必要により添加する材
料としてのグリオキザールやトリメチロールメラミンな
どは、OH基やCOOH基を有する上記高分子と化学結
合による架橋を形成して、成形物の耐水性を一層向上さ
せる。カオリン、ベントナイトなどの粘土鉱物も、難燃
化や硬度の調節に有用である。前述のようにフッ素系や
シリコーン系の樹脂コーティングは表面の撥水性、耐水
性を付与するのに貢献する。
The inorganic lightweight molded product of the present invention is composed of the above-mentioned inorganic compound, inorganic balloon, and three specific water-soluble polymer compounds, and glyoxal or trimethylolmelamine as a material to be added if necessary. And the like form crosslinks by chemical bonds with the above-described polymer having an OH group or a COOH group, and further improve the water resistance of the molded product. Clay minerals such as kaolin and bentonite are also useful for flame retardancy and hardness control. As described above, the fluorine-based or silicone-based resin coating contributes to imparting water repellency and water resistance to the surface.

【0028】以上のような構成からなる組成物は、無機
化合物や無機質バルーンが50重量%以上であっても、見
掛け密度0.4g/cm3以下の軽量成形物として良好な物性を
具備したものが得られる。ここで、無機質総容積率を20
%以上にし、加熱乾燥時の見掛けの容積収縮率(S)が30
%以下であると、亀裂の発生のない成形物が、非有機溶
媒系(水系)で得ることができる。
The composition having the above-mentioned composition has a good physical property as a lightweight molded product having an apparent density of 0.4 g / cm 3 or less even if the inorganic compound or the inorganic balloon is 50% by weight or more. can get. Where the total inorganic volume ratio is 20
% Or more, the apparent volumetric shrinkage ratio (S) during heat drying is 30
When it is at most%, a molded product free from cracks can be obtained in a non-organic solvent system (water system).

【0029】[0029]

【実施例】以下実施例により本発明を説明するが、本発
明はこれら実施例のみに限定されるものではない。 実施例1 固形分濃度48重量%のスチレン−ブタジエン共重合ラテ
ックス(以下SBRと略記)(共重合体のスチレン含有率
は約56重量%)104g、10重量%のPVA−217E(株式会
社クラレ製、0.4%の表面張力51mN/m)水溶液10g,1
0重量%のイソバン104(株式会社クラレ製、イソブチレ
ン−無水マレイン酸共重合物)水溶液6g,水120gを混
合した溶液に、ポルトランドセメント粉末(比重3.15)80
g、シラスバルーン(平均粒径0.1mm,嵩比重0.4)40gを
加え、家庭用ミキサーで10分間撹拌し泡立てたスラリー
(見掛け密度0.65g/cm3)をテフロンシート上、75℃で乾
燥成形し厚さ5mmの発泡シートを得た。このものは、気
泡構造は均一で、見掛け密度0.34g/cm3の亀裂のない表
面性良好なシートであった。シートの成形時の見掛けの
容積収縮率は8.8%、成形シートの全無機質量は70重量
%、容積率は25%であった。
EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Example 1 Styrene-butadiene copolymer latex having a solid content concentration of 48% by weight (hereinafter abbreviated as SBR) (the styrene content of the copolymer is about 56% by weight) 104 g, 10% by weight of PVA-217E (manufactured by Kuraray Co., Ltd.) , 0.4% surface tension 51mN / m) aqueous solution 10g, 1
0% by weight of Isoban 104 (manufactured by Kuraray Co., Ltd., isobutylene-maleic anhydride copolymer) 6 g of an aqueous solution and 120 g of water were mixed in a solution of Portland cement powder (specific gravity 3.15) 80
g, Shirasu balloon (average particle size 0.1 mm, bulk specific gravity 0.4) 40 g, and agitated with a household mixer for 10 minutes to create a foamed slurry.
(Apparent density 0.65 g / cm 3 ) was dried and molded on a Teflon sheet at 75 ° C. to obtain a foamed sheet having a thickness of 5 mm. This sheet was a sheet having a uniform cell structure and an apparent density of 0.34 g / cm 3 with no crack and good surface property. The apparent volumetric shrinkage during molding of the sheet was 8.8%, the total inorganic mass of the molded sheet was 70% by weight, and the volumetric ratio was 25%.

【0030】比較例1 シラスバルーンは添加せず、ポルトランドセメント粉末
120gを添加する以外は、実施例1とまったく同様に実
施した。気泡を保持したスラリー(見掛け密度0.62g/cm
3)より成形した発泡シートは、見掛け密度0.55g/cm
3で、大小の亀裂を持ったものであった。この場合の成
形時の見掛けの容積収縮率は46%と極めて大きく、成形
シートの無機質容積率は12%であった。
Comparative Example 1 Portland cement powder without addition of Shirasu balloon
The procedure was exactly the same as in Example 1 except that 120 g was added. Slurry holding air bubbles (apparent density 0.62 g / cm
The foamed sheet molded from 3 ) has an apparent density of 0.55 g / cm
At 3, it had large and small cracks. In this case, the apparent volumetric shrinkage rate at the time of molding was as large as 46%, and the inorganic volumetric rate of the molded sheet was 12%.

【0031】実施例2 固形分濃度が48重量%のSBR78g,10重量%のPVA
−420(株式会社クラレ製、0.4%の表面張力47mN/m)
水溶液7.5g,10重量%のイソバン104水溶液4.5g,水9
6gを混合した溶液に、木片セメント板の粉砕粉末(平均
粒径300μm)45g,シラスバルーン(平均粒径0.1mm,嵩
比重0.3)45gを加え家庭用ミキサーで10分間撹拌し泡立
てた。そのスラリーの見掛け密度は0.38g/cm3で、これ
をテフロンシート上85℃で乾燥し、厚さ5mm,見掛け密
度0.22g/cm3の良好な発泡シートを得た。この場合の成
形時の見掛けの容積収縮率は21%、成形シートの全無機
質量は70重量%、無機質容積率は21%であった。
Example 2 78 g of SBR having a solid content of 48% by weight and 10% by weight of PVA
-420 (Kuraray Co., Ltd., 0.4% surface tension 47 mN / m)
Aqueous solution 7.5 g, 10 wt% Isoban 104 aqueous solution 4.5 g, water 9
To a solution prepared by mixing 6 g, 45 g of crushed powder of wood chip cement plate (average particle size 300 μm) and 45 g of shirasu balloon (average particle size 0.1 mm, bulk specific gravity 0.3) were added and stirred with a household mixer for 10 minutes to foam. The apparent density of the slurry was 0.38 g / cm 3 , and this was dried on a Teflon sheet at 85 ° C. to obtain a good foamed sheet having a thickness of 5 mm and an apparent density of 0.22 g / cm 3 . In this case, the apparent volumetric shrinkage during molding was 21%, the total inorganic mass of the molded sheet was 70% by weight, and the inorganic volume ratio was 21%.

【0032】比較例2 シラスバルーンは用いず、木片とセメント粉末90gを添
加する以外は実施例2とまったく同様に行なった。気泡
を保持したスラリー(見掛け密度0.39g/cm3)より成形し
たシートは見掛け密度0.43g/cm3で亀裂の多いシートし
か得られなかった。この場合の成形時の見掛けの容積収
縮率は43%、成形シートの無機質容積率は10%であっ
た。
Comparative Example 2 The same procedure as in Example 2 was carried out except that wood particles and 90 g of cement powder were added without using Shirasu balloon. The sheet formed from the slurry holding air bubbles (apparent density 0.39 g / cm 3 ) had an apparent density of 0.43 g / cm 3 , and only a sheet with many cracks was obtained. In this case, the apparent volumetric shrinkage rate at the time of molding was 43%, and the inorganic volumetric rate of the molded sheet was 10%.

【0033】実施例3 固形分濃度が56重量%のエチレン−酢酸ビニル共重合エ
マルジョン(株式会社クラレ製、粒子荷電ノニオン、T
g=0℃、皮膜の引張強さ1.7MPa、破断伸び率1,500
%)89g,10重量%のPVA−420水溶液10g,10重量%
のポリビニルスルホン酸ソーダ水溶液6g,水134gを
混合した溶液に、ガラスビーズ(比重2.6平均粒径30μ
m)120g,バーミキュライト・バルーン(平均粒径0.5m
m,嵩比重0.15)40gを加え、実施例1と同様に発泡スラ
リー(見掛け密度0.56g/cm3)より成形し、厚さ5mm、見
掛け密度0.30g/cm3の良好な発泡シートを得た。成形時
の見掛けの容積収縮率は11%、成形シートの無機質含有
量70重量%、無機質容積率52%の良好なものが得られ
た。
Example 3 Ethylene-vinyl acetate copolymer emulsion having a solid content concentration of 56% by weight (Kuraray Co., Ltd., particle-charged nonion, T
g = 0 ° C, tensile strength of film 1.7MPa, elongation at break 1,500
%) 89 g, 10% by weight PVA-420 aqueous solution 10 g, 10% by weight
Glass beads (specific gravity 2.6 average particle diameter 30μ
m) 120g, vermiculite balloon (average particle size 0.5m
m, bulk specific gravity 0.15) 40 g was added and molded from a foamed slurry (apparent density 0.56 g / cm 3 ) in the same manner as in Example 1 to obtain a good foam sheet having a thickness of 5 mm and an apparent density of 0.30 g / cm 3 . . An excellent volumetric shrinkage rate of 11%, a molded sheet having an inorganic content of 70% by weight, and an inorganic volume ratio of 52% were obtained.

【0034】実施例4 固形分45.5%のメチルメタクリレート−ブタジエン共重
合ラテックス(以下MBRと略記)(共重合体中のメチル
メタクリレート含有率は約30重量%)110gとアニオン性
活性剤としてアルキルベンゼンスルポン酸ソーダ1.0g
を添加した他は実施例1と同様の組成及び方法で、厚さ
5mmの発泡シートとした。このものは、気泡構造が均一
で見掛け密度0.31g/cm3の亀裂のない表面性良好なシー
トであった。なお、シート成形時の見掛け容積収縮率が
9.1%、成形シートの全無機質量は69重量%、容積率は2
4.5%であった。
Example 4 110 g of methyl methacrylate-butadiene copolymer latex (hereinafter abbreviated as MBR) having a solid content of 45.5% (methyl methacrylate content in the copolymer is about 30% by weight) and alkylbenzene sulphone as an anionic activator. Acid soda 1.0 g
A foamed sheet having a thickness of 5 mm was prepared by the same composition and method as in Example 1 except that This was a sheet having a uniform cell structure, an apparent density of 0.31 g / cm 3, and no cracks and good surface properties. In addition, the apparent volumetric shrinkage during sheet formation
9.1%, total inorganic mass of molded sheet is 69% by weight, volume ratio is 2
4.5%.

【0035】実施例5 固形分濃度が48重量%のSBR78g,15重量%のメチル
セルロース水溶液(0.4%の表面張力39mN/m)5g,同
じく15重量%のヒドロキシエチルセルロース30g,水96
gを混合した溶液にカオリン粉末100gを、パーライト
バルーン(平均粒子径0.2mm,嵩比重0.38)40gを加え、
実施例1と同様にして厚さ約5mmの発泡シートを得た。
このものは気泡構造が均一で、見掛け密度0.35g/cm3
亀裂のない表面性良好な白色シートであった。シート成
形時の見掛け容積収縮率は11%、成形シートの全無機質
量は76.6重量%、容積率は21%であった。
Example 5 78 g of SBR having a solid content of 48% by weight, 5 g of a 15% by weight aqueous solution of methylcellulose (0.4% of surface tension 39 mN / m), 30 g of 15% by weight of hydroxyethyl cellulose and 96 of water.
Kaolin powder (100 g) and pearlite balloon (average particle size 0.2 mm, bulk specific gravity 0.38) 40 g were added to the mixed solution of g,
A foamed sheet having a thickness of about 5 mm was obtained in the same manner as in Example 1.
This was a white sheet having a uniform cell structure and an apparent density of 0.35 g / cm 3 with no cracks and good surface properties. The apparent volumetric shrinkage rate during sheet molding was 11%, the total inorganic mass of the molded sheet was 76.6% by weight, and the volumetric rate was 21%.

【0036】以上の実施例1〜5及び比較例1,2で用
いた接着剤のラテックス、エマルジョンの高分子化合物
の凝集エネルギー密度は、いずれも50〜150(cal/cc)の
範囲のものである。
The cohesive energy densities of the latex of the adhesive and the polymer compound of the emulsion used in Examples 1 to 5 and Comparative Examples 1 and 2 are in the range of 50 to 150 (cal / cc). is there.

【0037】[0037]

【発明の効果】本発明に係る無機質系軽量成形物は、以
上のような特定の組成物で構成するため、まったく新し
い材料のみならず、無機系製品の加工屑や各種無機系成
形物の廃材なども粉末状態にして原料として利用するこ
とができ、リサイクルによる資源活用となる。また発泡
軽量組成物として耐熱性、不燃性を保持した上に軽量か
つ柔軟性を有する優れた性質のものが得られるので、断
熱材、緩衝材、吸音材、吸着材、フィルター材、各種積
層複合用材料などとして、安価に各種の産業分野で広範
囲に再利用できる製品となる。
EFFECTS OF THE INVENTION Since the inorganic light-weight molded product according to the present invention is composed of the above specific composition, it is not only a completely new material, but also processing scraps of inorganic products and waste materials of various inorganic molded products. It can also be used as a raw material in powder form and can be used as a resource by recycling. In addition, since it is possible to obtain a foamed lightweight composition having excellent properties such as light weight and flexibility while maintaining heat resistance and nonflammability, a heat insulating material, a cushioning material, a sound absorbing material, an adsorbing material, a filter material, various laminated composites. It becomes a product that can be widely reused in various industrial fields at low cost as a material for use.

【0038】本発明による無機質系軽量成形物は、連続
気泡による気孔率が30〜80%となるが、中空体であるバ
ルーンを併用するためバルーンに基づく独立気泡も同時
に所有することになり、中空無機質と多孔有機質との両
者の特徴を兼ね備えることになる。製造方法も湿式法で
有機溶媒を使用しないので、極めて安全かつ簡潔安価な
方法である。
The inorganic lightweight molded product according to the present invention has a porosity of 30 to 80% due to open cells, but since it also uses a hollow balloon, it also possesses closed cells based on the balloon. It has both the characteristics of the inorganic material and the porous organic material. Since the manufacturing method is a wet method and does not use an organic solvent, it is a very safe, simple and inexpensive method.

【図面の簡単な説明】[Brief description of drawings]

【図1】本発明の無機質系軽量成形物の製造工程を示す
フローチャートである。
FIG. 1 is a flow chart showing a manufacturing process of an inorganic lightweight molded article of the present invention.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 井本 三郎 兵庫県宝塚市中山台2丁目6番8号 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Saburo Imoto 2-6-8 Nakayamadai, Takarazuka-shi, Hyogo

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】 1成分として粒径5〜1,000μm、嵩比
重0.8以下の無機質バルーンを含む無機化合物と、皮膜
の引張強さ10〜300MPa、かつ20℃における濃度0.4重量
%水溶液の表面張力30〜65mN/mで、1分子中に水酸
基2個以上を有する水溶性の高分子化合物と、1分子中
に2個以上のカルボキシル基またはスルホン基を有する
水溶性の高分子化合物又は/及びアニオン性界面活性剤
と、皮膜の引張強さ0.1〜10MPa,破断伸び率200〜2,00
0%、2次転移温度−40〜30℃、かつ凝集エネルギー密
度30〜200cal/ccである高分子化合物の組成物よりなる
無機質系軽量成形物。
1. An inorganic compound containing an inorganic balloon having a particle size of 5 to 1,000 μm and a bulk specific gravity of 0.8 or less as one component, a film tensile strength of 10 to 300 MPa, and a surface tension of an aqueous solution of 0.4% by weight at 20 ° C. 30 -65 mN / m, water-soluble polymer compound having two or more hydroxyl groups in one molecule, and water-soluble polymer compound having two or more carboxyl groups or sulfone groups in one molecule and / or anionic Surfactant, film tensile strength 0.1-10MPa, elongation at break 200-2,00
An inorganic lightweight molded product made of a composition of a polymer compound having a second-order transition temperature of −40 to 30 ° C. and a cohesive energy density of 30 to 200 cal / cc.
【請求項2】 無機化合物と、皮膜の引張強さ10〜300
MPa、かつ20℃における濃度0.4重量%水溶液の表面張
力30〜65mN/mで、1分子中に水酸基2個以上を有す
る水溶性の高分子化合物を無機化合物に対し0.5〜10重
量%と、1分子中に2個以上のカルボキシル基またはス
ルホン基を有する水溶性の高分子化合物又は/及びアニ
オン性界面活性剤を無機化合物に対し0.5〜20重量%
と、皮膜の引張強さ0.1〜10MPa、破断伸び率200〜2,00
0%、2次移転温度−45〜30℃、かつ凝集エネルギー密
度30〜200cal/ccである高分子化合物を無機化合物に対
し5〜100重量%の組成物よりなり、かつ無機化合物の
1成分として粒径5〜1,000μm嵩比重0.8以下の無機質
バルーンを成形物中の無機質総容積率が20%以上及び成
形時の見掛けの容積収縮率が30%以下になるように添加
することを特徴とする無機化合物含量50重量%以上、見
掛け密度0.4g/cm3以下の無機質系軽量成形物。
2. An inorganic compound and a film having a tensile strength of 10 to 300.
A water-soluble polymer compound having a surface tension of 30 to 65 mN / m at a concentration of 0.4 wt% aqueous solution at 20 ° C. of MPa of 0.5 to 10 wt% with respect to an inorganic compound and a water-soluble polymer compound of 1 to 2 is included. 0.5 to 20% by weight of a water-soluble polymer compound having two or more carboxyl groups or sulfone groups in the molecule or / and an anionic surfactant based on the inorganic compound
And the tensile strength of the film is 0.1-10MPa, the elongation at break is 200-2,00
0%, a secondary transfer temperature of −45 to 30 ° C., and a cohesive energy density of 30 to 200 cal / cc, composed of a composition of 5 to 100% by weight with respect to an inorganic compound, and as a component of the inorganic compound. Characterized by adding an inorganic balloon having a particle size of 5 to 1,000 μm and a bulk specific gravity of 0.8 or less so that the total volume ratio of the inorganic material in the molded product is 20% or more and the apparent volumetric shrinkage ratio during molding is 30% or less. An inorganic lightweight molded product having an inorganic compound content of 50% by weight or more and an apparent density of 0.4 g / cm 3 or less.
JP10754895A 1995-05-01 1995-05-01 Inorganic lightweight foam molding Expired - Fee Related JP3561728B2 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015510027A (en) * 2012-03-16 2015-04-02 スリーエム イノベイティブ プロパティズ カンパニー Lightweight article, composite material composition, and method of manufacturing the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015510027A (en) * 2012-03-16 2015-04-02 スリーエム イノベイティブ プロパティズ カンパニー Lightweight article, composite material composition, and method of manufacturing the same

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