JP2001058815A - Molding precursor of aqueous film-forming inorganic compound increased in molecular weight and molding thereof - Google Patents

Molding precursor of aqueous film-forming inorganic compound increased in molecular weight and molding thereof

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Publication number
JP2001058815A
JP2001058815A JP11272897A JP27289799A JP2001058815A JP 2001058815 A JP2001058815 A JP 2001058815A JP 11272897 A JP11272897 A JP 11272897A JP 27289799 A JP27289799 A JP 27289799A JP 2001058815 A JP2001058815 A JP 2001058815A
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Japan
Prior art keywords
inorganic compound
aqueous film
forming inorganic
molding
less
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JP4291468B2 (en
Inventor
Hiroshi Kokuta
博 穀田
Katsuhiro Kokuta
勝洋 穀田
Hideaki Uchida
秀明 内田
Kenji Kokuta
憲治 穀田
Naoto Kokuta
直人 穀田
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Abstract

PROBLEM TO BE SOLVED: To replace a synthetic resin and foams or FRPs especially in fear of combustion and disposal pollution with an inorganic substance and reduce the pollution by using a molding precursor of an inorganic polymer exhibiting a thermoplastic behavior. SOLUTION: A high-molecular weight aqueous film-forming inorganic compound which is a substance composed of an aqueous siloxane or a silanol and has >=1,000, practically >=4,000 weight-average molecular weight at >=2 molar ratio of SiO2/Na2O is converted into an alkoxide and formed into fine particles to thereby provide a molding precursor. The resultant precursor can optionally be regulated to a powder size without sticking or fusing even when water is included therein. As a result, an incombustible molded product capable of carrying out stable type disposal treatment can be molded according to a conventional method for molding synthetic resins.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【産業上の利用分野】石油化学とその高分子化学は,国
民生活に多大の利便をもたらしたが,また同時に環境ホ
ルモンやダイオキシン,重金属などの公害物質を発生さ
せ,今日まで多大の堆積を生じている。また,その廃棄
焼却処理の際に発生する黒煙や悪臭や排ガスは,居住環
境に悪影を響を与えており,一方リサイクル使用を進め
ているが,基本的な解決には至らず,無公害品を求めて
いても実現していない。無機物で作られた,塗布材や成
型材,膜材,板材または断熱・包装材があれば,居住環
境に揮発性物や環境ホルモンを発生することなく,防災
上からもまた居住環境上の健康製品になる。また無機製
品であれば,投棄しても土に還元して安全製品となり,
合成樹脂に代替して膨大な利用分野がある。合成樹脂
は,熱可塑性であったから生産性は高かった。従来不可
能視されていた,無機化合物が,熱可塑性になれば,合
成樹脂と同様の成形量産化を実現するこが可能となる
が,未だ実現していない。
[Industrial applications] Petrochemicals and their macromolecular chemistry have brought great convenience to the people's lives, but at the same time generate pollutants such as environmental hormones, dioxins, and heavy metals, and have caused a great deal of accumulation to date. ing. In addition, the black smoke, odor and exhaust gas generated during the waste incineration process have a bad influence on the living environment. On the other hand, recycling is being promoted, but the basic solution has not been reached. It has not been realized even if it seeks pollution products. If there is a coating material, a molding material, a film material, a board material, or a heat insulating / packaging material made of inorganic materials, no volatile substances and environmental hormones are generated in the living environment, and the health of the living environment as well as disaster prevention. Become a product. Also, if it is an inorganic product, even if it is dumped, it is reduced to soil and becomes a safe product.
There are enormous fields of use in place of synthetic resins. The productivity was high because the synthetic resin was thermoplastic. If inorganic compounds, which had been considered impossible in the past, become thermoplastic, it will be possible to realize the same mass production as synthetic resins, but this has not yet been achieved.

【0002】[0002]

【従来の技術】無機物の熱可塑性材は,ガラスである
が,可塑化温度は高温であり,また合成樹脂のような成
形量産性を生じない。珪酸ソーダがあるが,強アルカリ
性で,小分子量しかなく,コロイドであるから,乾燥し
ても微細観察すると,空隙があり,吸湿しやすく日常使
用品にはならない。更に燐酸系やアルコキシド系がある
が,熱可塑性にはならず造膜硬化性能は十分ではない。
2. Description of the Related Art An inorganic thermoplastic material is glass, but its plasticization temperature is high, and it does not produce molding mass productivity like a synthetic resin. Although sodium silicate is available, it is strongly alkaline, has only a small molecular weight, and is a colloid. When it is dried and observed finely, it has voids and easily absorbs moisture, making it not a daily use product. Further, there are phosphoric acid and alkoxide compounds, but they do not have thermoplasticity and film formation hardening performance is not sufficient.

【0003】水性で造膜性あるのは,合成樹脂のPVA
があるが耐水性なく,また合成樹脂を懸濁して塗剤と
し,水を蒸発して皮膜を形成するエマルジョンがあり,
ラテックス水性塗料は,固形分を懸濁して50%以上に
しているが,廃棄燃焼に問題あり,無公害の無機化合物
の水性塗料はない。シリコン樹脂であっても組成有機物
は,燃焼して黒煙を生じ悪臭を生じ,その廃棄処理に困
っている。
An aqueous and film-forming material is a synthetic resin PVA.
There is an emulsion that is not water-resistant, and also has a synthetic resin suspended as a coating and water is evaporated to form a film.
Latex water-based paints have a solid content suspended to 50% or more, but there is a problem with waste combustion, and there is no water-based paint of non-polluting inorganic compounds. Even in the case of silicon resin, the composition organic matter burns to produce black smoke and produces a bad smell, and it is difficult to dispose of it.

【0004】常温発泡には,A液とB液を混合して反応
発泡するウレタン樹脂が重用されているが,火災や現場
溶接作業での火災で大きな災害を発生し問題となってい
る。
A urethane resin that reacts and foams by mixing the liquid A and the liquid B is used for room temperature foaming. However, a fire or a fire caused by welding at a site causes a serious disaster and causes a problem.

【0005】[0005]

【従来技術の問題点】従来の合成樹脂系成型品は,防災
上安全な製品ではない。発泡スチロールと発泡ウレタン
は黒煙と悪臭を上げて燃焼し,燃焼ガスで死亡する例が
多く,フエノールや尿素樹脂も燃焼してホルマリンを発
生し,防災上好ましくない。ポリエチやポリプロ成形体
は容易に燃焼する。即ち従来の合成樹脂やその発泡体に
防災上問題あり,また健康上環境ホルモンを発生するも
のもあり,投棄しても土に還元しないものばかりであ
る。水性無機物,例えば水ガラス1号は,モル比がSi
/Na=1.03で分子量(以後重量平均分子量をい
う)は140以下にすぎず高粘性物となり,高分子とい
う定義の最低分子量値1000に至らず,また耐水性を
生じなかった。前記モル比を2以上にするに従い増粘
し,500CP以下の低粘度にはできなかった。
2. Description of the Related Art Conventional synthetic resin molded products are not safe products for disaster prevention. Styrofoam and urethane foam burn with black smoke and foul odor, and are often killed by the combustion gas. Phenol and urea resin also burn to generate formalin, which is not preferable for disaster prevention. Polyethylene and polypropylene moldings burn easily. That is, conventional synthetic resins and their foams have problems in disaster prevention, and some of them generate environmental hormones in health, and even if they are dumped, they are not reduced to soil. Aqueous inorganic substances, for example, water glass No. 1, have a molar ratio of Si
When /Na=1.03, the molecular weight (hereinafter referred to as the weight average molecular weight) was only 140 or less, resulting in a highly viscous substance, not reaching the minimum molecular weight of 1000 defined as a polymer, and no water resistance. As the molar ratio was increased to 2 or more, the viscosity increased, and a low viscosity of 500 CP or less could not be obtained.

【0006】ALCやセメント発泡体やセラミック発泡
体はあるが,軽薄にはならず,また生産には長時間の高
温養生を要した。合成樹脂を成型するような高サイクル
成型はできなかった。
[0006] Although there are ALC, cement foam and ceramic foam, they do not become light and light and require long-term high-temperature curing for production. High cycle molding such as molding of synthetic resin could not be performed.

【0007】[0007]

【発明が解決しようとする課題】本発明は,合成樹脂製
品のように軽量で,生産性よく製造できて,脆化せずハ
ンドリング強度あり,不燃で火災に安全で,投棄して
も,土に還元しうる無機成型体を製造する材料と成型法
を提案する。即ち,これを実現する材料は,水性で,通
常高分子と称しうる,1000以上の高分子量のある,
水性熱可塑性造膜性無機化合物でなければならない。
DISCLOSURE OF THE INVENTION The present invention relates to a light-weight synthetic resin product, which can be manufactured with good productivity, does not become brittle, has a handling strength, is nonflammable, is safe against fire, and can be dumped in soil. We propose a material and a molding method for producing a reducible inorganic molded body. That is, the material to realize this is water-based, which can be generally referred to as a polymer, and has a high molecular weight of 1,000 or more.
It must be an aqueous thermoplastic film-forming inorganic compound.

【0008】使用材に揮発性物なく健康的で,火災に安
全で,燃焼しても,有害な排ガスを発生しないのは,水
性の無機物であり,低温造膜性あれば成型性を生じ,重
金属を含有しない無機物は投棄しても,植物の必須栄養
成分となり,土壌に還元するので公害を生じない。布や
木材に含浸処理すれば持続性防火材になる。
[0008] It is an aqueous inorganic substance that is healthy without volatile substances, safe to fire, and does not emit harmful exhaust gas when burned. Even if the inorganic substances that do not contain heavy metals are discarded, they become essential nutrients for plants and reduce them to the soil, so that they do not cause pollution. Impregnating fabric or wood can be a persistent fire protection material.

【0009】合成樹脂と同様の成型性を得るためには,
成型造膜性あり,高分子量のある,熱可塑性高分子アモ
ルフアス水性造膜性無機化合物でなければならない。
In order to obtain the same moldability as synthetic resin,
It must be a thermoplastic polymer amorphous aqueous film-forming inorganic compound that has film-forming properties and high molecular weight.

【0010】本発明者等が提案した 特許第20282
03号「水性造膜性無機化合物」は,結晶質原料を使用
しながら非晶質(アモルフアス)高濃度水性無機化合物
にした新規な物である。
Patent No. 20282 proposed by the present inventors.
No. 03 "Aqueous film-forming inorganic compound" is a novel compound obtained by converting a crystalline raw material into an amorphous (amorphous) high-concentration aqueous inorganic compound.

【0011】前記「水性造膜性無機化合物」は,アルカ
リ性のシラノールとシロキサンのダイマーやトリマー以
上の混合物である,アモルフアス高濃度水性造膜性無機
化合物(以後MFと略称する)である。金属シリコンと
高濃度アルカリ金属とを接触反応せしめる際,弗化ソー
ダや硼砂,亜硫酸塩,亜硝酸塩,亜燐酸塩のいずれか又
は複合して存在せしめ,60度以上実際には80度以上
を維持するように自己発熱せしめ,または加熱して反応
生成した,保有水が80%以内の水性造膜性無機化合物
である。常圧下での前記生成物は,電子顕微鏡の100
0倍で観察したが,約1ミクロンのコロイドであった。
水性材は加熱脱水硬化しても,吸湿して脆化する所謂も
どり現象の欠点があった。
The above-mentioned "aqueous film-forming inorganic compound" is an amorphous high-concentration aqueous film-forming inorganic compound (hereinafter abbreviated as MF), which is a mixture of a dimer or a trimer of an alkaline silanol and a siloxane. When metal silicon and high concentration alkali metal are contact-reacted, sodium fluoride, borax, sulfite, nitrite, or phosphite are present or in a complex state. It is an aqueous film-forming inorganic compound having a water content of 80% or less, which is self-generated or heated by heating. Under normal pressure, the product was analyzed by electron microscopy.
Observed at 0 magnification, it was a colloid of about 1 micron.
The aqueous material has a drawback of a so-called return phenomenon in which even if it is heated, dehydrated and hardened, it absorbs moisture and becomes brittle.

【0012】本発明者等は,鉄板にLCを塗り,高温顕
微鏡で,常温から1000度Cまで昇温しながら観察し
た。200度までは余剰水が蒸気になり接眼鏡を曇らし
たが,同時に発泡状態を観察できた。600度では泡石
状を示し,900度では水飴状にペースト化した。冷却
した塗膜はフリットと同様であった。
The present inventors applied LC on an iron plate and observed it with a high-temperature microscope while increasing the temperature from room temperature to 1000 ° C. Up to 200 degrees, the excess water turned into steam and clouded the eyepiece, but at the same time a foaming state could be observed. At 600 ° C., it was foamed, and at 900 ° C., it was pasted into syrup. The cooled coating was similar to a frit.

【0013】上記LCの塗布物のFTIR分析を別紙第
1図(常温塗布直後)・第2図(塗布後2時間)に示し
た。常温放置して左端の水酸基ピークを減少するのは,
常温で造膜能あることを示している。これを加熱する
と,バブル状に発泡して,また600度近辺でオパール
(泡石)になり,スムースな表面を形成しない。また表
面が低温造膜していると,内部の乾燥が十分にならず,
ベトつき,水に再溶解する原因になっている。
The FTIR analysis of the LC coated material is shown in FIGS. 1 (immediately after coating at room temperature) and 2 (2 hours after coating). The decrease in the hydroxyl peak at the left end after leaving at room temperature
It shows that it has a film forming ability at room temperature. When this is heated, it foams into a bubble and turns into opal (foam stone) at around 600 degrees, and does not form a smooth surface. Also, if the surface is formed at low temperature, the inside cannot be dried sufficiently,
It is sticky and causes redissolution in water.

【0014】保有水が50重量部以上あると,加温して
も表面に造膜物あるため,余剰水は蒸発しないので濃縮
しがたい。濃縮を早めるため高温加熱すると,造膜発泡
しやすく,常圧で固形分を50%以上の溶液にするの
に,100度以下の低温加熱して長時間を要した。
If the water content is more than 50 parts by weight, the surplus water does not evaporate because of the formation of a film on the surface even when heated. When heated at a high temperature to accelerate the concentration, film formation and foaming are apt to occur, and it takes a long time at a low temperature of 100 ° C. or less to form a solution having a solid content of 50% or more at normal pressure.

【0015】合成樹脂の成型は,熱硬化か熱可塑性を利
用し高サイクル成型が可能であるが,水性造膜物には,
加熱すれば水蒸気を発生するので,この原理を適用しが
たく,加熱脱水硬化成型するために,合成樹脂のような
ペレットやビーズあるいはシート状にすればよいが,見
かけ上,水分なくて相互に付着しない状態にしなければ
作業性なく,保有水を40%以下の製品にしても前記吸
湿もどり性あれば,均一な注型はできず,生産は困難で
ある。
[0015] High cycle molding is possible by using thermosetting or thermoplasticity for molding of synthetic resin.
When heated, water vapor is generated, so this principle is difficult to apply. For heat dehydration and hardening, pellets, beads, or sheets, such as synthetic resin, may be used. If it does not adhere, there is no workability, and even if the product has a water content of 40% or less, uniform casting cannot be performed if the moisture absorption and reversion is used, and production is difficult.

【課題を解決するための手段】[Means for Solving the Problems]

【0016】上記MFの保有水の温度別減水量を分析試
験した結果を下記に示す。本発明の保有水とは,100
0度C加熱した場合の脱水量をゆう。 通常 樹脂や木材の水分測定は,100〜110度Cで
3時間加温した残存物から算定しているので,本数値と
は異なっている。150度以上に加熱すれば30%以下
の保有水となる。実際には200〜300度の温度範囲
で可能である。200度Cに加熱すれば,第1表から,
保有水は 3.7%になり,固体化する。
The results of an analytical test of the amount of water loss of the MF possessed water by temperature are shown below. The water possessed by the present invention is 100
The amount of dehydration when heating at 0 ° C. is determined. Normally, the moisture measurement of resin and wood is calculated from the residue heated at 100 to 110 ° C for 3 hours. If heated to 150 degrees or more, the water content will be less than 30%. Actually, it is possible in the temperature range of 200 to 300 degrees. If heated to 200 degrees C, from Table 1,
The retained water becomes 3.7% and solidifies.

【0017】水性造膜性無機化合物は,上述したFTI
R(第1,2図)の通り左端の水分子ピークは減少し常
温造膜性あるので,脱水のため加熱すると,固体の砂糖
が熱水にとけ造粘し,可塑化物となり,造膜し水が発泡
剤になり,カルメラ焼きしたと同様に,発泡固体化す
る。
The aqueous film-forming inorganic compound is the same as the above-mentioned FTI
As shown in R (Figs. 1 and 2), the water molecule peak at the left end decreases and has room temperature film-forming properties, so when heated for dehydration, solid sugar melts in hot water and becomes viscous, forming a plasticized product and forming a film. The water becomes a foaming agent, and becomes foamed and solidified in the same manner as caramel baked.

【0018】成型前駆物になすには,造形粘土状の高ゲ
ル体か軟質合成樹脂シート状にしなければならないが,
之を得るためには,加熱発泡を抑えた常圧で100度以
上に相当する,加圧加熱法か減圧加熱法を使用し,保有
水分を30%以内に減水し,水もどり性がないようにし
なければ成型前駆物にはならない。この製品ができれば
加熱硬化し成型できる。
In order to form a molding precursor, it is necessary to form a molded clay-like high gel body or a soft synthetic resin sheet.
In order to obtain this, use the pressure heating method or the reduced pressure heating method, which is equivalent to 100 degrees or more at normal pressure while suppressing heating and foaming, reduce the water content to 30% or less, and make sure that there is no water reversion. Otherwise, it will not be a molding precursor. If this product is made, it can be cured by heating and molded.

【0019】上記加圧加熱法で濃縮すると,常圧濃縮で
は,アモルフアスであってもコロイドは消失しないが,
加圧加熱すると,ダイマーとトリマーの水性造膜性無機
化合物は,重量平均分子量が5000以上の塗膜状に高
分子化した。1号水ガラスは140以下の分子量にすぎ
ない。本発明の塗膜からは,2000〜5000倍の電
子顕微鏡(SEM第3図)観察しても,コロイドは発見
されず合成樹脂高分子と同様の塗膜状物になっていた。
When concentrated by the above-mentioned heating under pressure, the colloid does not disappear even in the case of amorphous in the concentration under normal pressure.
When heated under pressure, the aqueous film-forming inorganic compounds of dimer and trimer were polymerized into a coating film having a weight average molecular weight of 5000 or more. No. 1 water glass has a molecular weight of only 140 or less. Even when observed with an electron microscope (SEM, FIG. 3) at 2000 to 5000 magnification, the coating film of the present invention did not show any colloid, and was in the form of a coating film similar to a synthetic resin polymer.

【0020】加圧加熱は,通常の1〜20K/cm2
加圧のオートクレーブを使用し,従って,常圧で60〜
100度Cであっても,加圧下では100〜200度C
の間に相当し。実際に100〜160度Cで分子量は,
5000〜10,000に高分子化した。
The heating under pressure is performed in the usual range of 1 to 20 K / cm2.
Use a pressurized autoclave;
100-200 ° C under pressure, even at 100 ° C
Between the equivalent. Actually at 100-160 ° C the molecular weight is
It was polymerized to 5000 to 10,000.

【0021】常圧で,上述At normal pressure,

【0011】に記載した反応をするとPH12前後の強
アルカリ性物となる。低アルカリにするべくアルカリ金
属量を減らすと,反応は弱く,固形分濃度をあげるの
に,加温しても長時間を要した。後に実施例で示すが,
加温し反応し未反応物の多い溶液を,加圧加熱容器中で
反応せしめると,容易にPH10〜12の水性造膜性無
機溶液を製造できた。電子顕微鏡観察しても,コロイド
は消失し高分子状に塗膜化していた。
When the reaction described in the above is carried out, a strongly alkaline substance having a pH of about 12 is obtained. When the amount of alkali metal was reduced to reduce the alkali, the reaction was weak, and it took a long time to heat up the solid content even after heating. Later in the examples,
By heating and reacting the solution containing many unreacted substances in a pressurized and heated vessel, an aqueous film-forming inorganic solution having a pH of 10 to 12 could be easily produced. Electron microscopic observation revealed that the colloid had disappeared and was formed into a polymer film.

【0022】これら硬化体の耐水性は,モル比が2以上
で,確実には3以上で200度以上に加熱すれば得られ
た。80度以上で常圧製造した製品で比重1.4製品を
紙コップに50gとり,電子レンジ(250W)で5分
間200度以上に加熱し,無機発泡体を得た。湿度80
%室内に1日放置したところ,常圧製造品表面は吸水あ
りベタ付きを生じたが,本発明のモル比が3以上の加圧
製造成型品表面からは,吸水ベタ付き現象はなかった。
The water resistance of these cured products can be obtained by heating at a molar ratio of 2 or more and certainly at 3 or more to 200 ° C. or more. A product prepared at normal pressure at 80 ° C. or higher and having a specific gravity of 1.4 was taken in a paper cup and heated to 200 ° C. or more for 5 minutes in a microwave oven (250 W) to obtain an inorganic foam. Humidity 80
%, The surface of the product under normal pressure produced water absorption and became sticky when left in a room for 1 day, but the surface of the molded product under pressure having a molar ratio of 3 or more according to the present invention did not show any water absorbing solid content.

【0023】本発明に使用する水性造膜性無機化合物
は,原料に金属シリコンを大過剰に配合するとアルカリ
金属や弗化ソーダやアルカリ性の硼砂を配合しても,P
H値が12以下になるまで激しく反応合成して,Si/
Na比は,約2以上になったが,粘度は100〜200
センチポイズにすぎず,1号水ガラスのような造粘性は
なく,PHは12〜11となった。
In the aqueous film-forming inorganic compound used in the present invention, when a large excess of metallic silicon is added to the raw material, even if an alkali metal, sodium fluoride or alkaline borax is added,
A vigorous reaction synthesis was performed until the H value became 12 or less.
Although the Na ratio became about 2 or more, the viscosity was 100 to 200.
It was only centipoise and did not have the viscosifying properties of No. 1 water glass, and the PH was 12-11.

【0024】上述配合で,釉薬配合(後述第3表比較
図)に近似させた場合に,または前述触媒に硼砂を使用
した時,硼酸化合物と反応するオキシ酸化合物やポリア
ミン化合物を混合すると,常圧でハイブリッド化した。
エチレングリコール(ポリかジ)やプロピレングリコー
ルを混合すると,コロイドをコートした。グアニジン化
合物の炭酸グアニジンを加えてハイブリッド化した。
In the above-mentioned composition, when an oxyacid compound or a polyamine compound which reacts with a boric acid compound is mixed when the glazing composition is approximated to a glaze composition (comparison table in Table 3 below), or when borax is used as the above-mentioned catalyst, the mixing is usually performed. Hybridized with pressure.
Mixing ethylene glycol (polydiene) or propylene glycol coated the colloid. The guanidine compound guanidine carbonate was added for hybridization.

【0025】Si/Na比を3以上にし,PHを12以
下例えば11.7にすると,保有水が大過剰の80%以
内であっても,加熱脱水すれば,その加熱硬化物は,耐
水化した。
When the Si / Na ratio is set to 3 or more and the PH is set to 12 or less, for example, 11.7, even if the retained water is within 80% of a large excess, the heat-cured product can be made water-resistant by dehydrating by heating. did.

【0026】前掲特許第202820号の水性造膜性無
機化合物で,低濃度であっても1価メチルアルコールを
混合するとゲル化は早いが,2価以上のイソプロピルア
ルコール(IPA)を混合すると固形分相当分が造粘沈
下し濃縮するので,それを取り出し簡易濃縮する方法を
説明した。沸点200度以下のヒドロキシルオール化合
物は前述アルカリ金属を含有する水性造膜性無機化合物
とアルコキシド化合物となるが,例えば多価エチレング
リコールを混合すると造粘し,ポリエチレングリコール
の分子量400〜600物を10〜20%混合すると,
造粘疎水化することを見いだした。即ち,1価のメチル
アルコールと多価のポリエチレングリコール(ポリエチ
レンオキシド..理化学辞典第3版)の混合液に,前述
水性造膜性無機化合物を,又はそれに前記混合液を混合
して,スプレーすれば,微細粒となり回収でき,滴下す
ればビーズ化し,切断落下させればペレット状で回収で
きた。これを乾燥すれば,保水性のある固化体となっ
た。加熱すれば可塑化し,保有水が5%以下となれば硬
化体となった。ポリエチレングリコールの高分子(6,
000〜10,000)を使用すると,発泡しても合成
樹脂以上の強度を生じた。CaやMgイオンとなる石灰
や炭カル,ドロマイトを加えて更に加熱して重合体とな
った。上記手法で粒子化した場合水分を保有しながら密
閉包装しても付着や融着物を生じなかった。アルコキシ
ド形成物の1価アルコールはメタ,エチル,プロパン,
ブタン,ペンタン,ヘキサン,ヘプタン,オクタン,ノ
ニル,ラウリル,ミリスチル,セチル,ステアリル,オ
レイルアルコールなどだあり,2価にはエチレン,プロ
ピレングリコールやブタン,ペンタンジオール,ヘキサ
ン,ヘプタン,オクタンジオールやネオペンチルグリコ
ールあり,3価以上にはグリセリン,トリメチロールプ
ロパン,ペンタエリスリトールやソルビタン等がある
が,沸点が200度以下か水または前記ヒドロキシオー
ルに均一混合できるものがのぞましい。
The aqueous film-forming inorganic compound disclosed in the above-mentioned Patent No. 202820. Even if the concentration is low, gelation is rapid when monohydric methyl alcohol is mixed, but the solid content is high when divalent or higher isopropyl alcohol (IPA) is mixed. Since a considerable amount of slime was formed and concentrated, the method of taking it out and condensing it easily was explained. The hydroxylol compound having a boiling point of 200 ° C. or less becomes the above-mentioned aqueous film-forming inorganic compound containing an alkali metal and an alkoxide compound. If you mix ~ 20%
It has been found that the viscosities are converted to visco-hydrophobicity. That is, the aqueous film-forming inorganic compound described above, or a mixture thereof, is mixed with a mixture of monovalent methyl alcohol and polyvalent polyethylene glycol (polyethylene oxide, the third edition of the Physical and Chemical Dictionary), and sprayed. If it was dropped, it could be collected as fine particles, dropped into beads, and cut and dropped into pellets. When this was dried, it became a solid with water retention. It was plasticized when heated, and became a cured product when the water content was 5% or less. Polymer of polyethylene glycol (6
000 to 10,000), even when foamed, the strength was higher than that of the synthetic resin. Lime, which becomes Ca and Mg ions, charcoal and dolomite were added, and the mixture was further heated to obtain a polymer. When the particles were formed by the above-mentioned method, no adhesion or fusion occurred even when the container was sealed and sealed while retaining moisture. The monohydric alcohol of the alkoxide-forming product is meta, ethyl, propane,
Butane, pentane, hexane, heptane, octane, nonyl, lauryl, myristyl, cetyl, stearyl, oleyl alcohol, etc., divalent ethylene, propylene glycol, butane, pentanediol, hexane, heptane, octanediol and neopentyl glycol There are trivalent or higher glycerin, trimethylolpropane, pentaerythritol, sorbitan, etc., but those having a boiling point of 200 ° C. or lower or those which can be uniformly mixed with water or the hydroxyol are preferable.

【0027】1年草の綿や麻を補強材にし,これに前項
(0025)の水性造膜性無機化合物を含浸し保有水を
40%以下にした未硬化成型SMC(sheet mo
ulding compound)やBMC(bulk
moulding compound)は,加熱加圧
硬化成型することができのでFRP代替成型前駆物にな
った。繊維はガラスや岩綿・カーボン繊維などの無機繊
維やポバール・プロピレン・ナイロン・ポリイミドなど
の有機繊維でも可能であるが,投棄廃棄した場合土に還
元する無限資源の1年草がよい。
An uncured molded SMC (sheet moat) in which annual cotton or hemp is used as a reinforcing material and impregnated with the aqueous film-forming inorganic compound described in the above item (0025) to reduce the water content to 40% or less.
ulding compound) and BMC (bulk)
The molding compound was a precursor to FRP substitute molding because it can be molded by heating and pressing. The fibers can be inorganic fibers such as glass, rock wool, and carbon fibers, or organic fibers such as poval, propylene, nylon, and polyimide. However, it is preferable to use an infinite annual resource that is reduced to soil when discarded.

【0028】前記(0026)記載の造膜性無機化合物
を,保有水を30%以下に濃縮すると,合成樹脂のよう
にペレットにすることができた。それを注型し加熱する
と,前記造膜性無機化合物は高分子になっているため,
合成樹脂が可塑化したと同様な塑性物になり,保有水が
蒸発し発泡剤となり,造膜を破ることなく発泡体になっ
た。比重は1以下で,標準的には0.3〜0,5になっ
た。アルカリ金属含有量多い場合はエチレングリコール
を,含有量が少ない場合はポリエチレングリコールを選
択使用すると製造作業性はよい。
When the water content of the film-forming inorganic compound described in (0026) was reduced to 30% or less, pellets could be formed like synthetic resin. When it is cast and heated, the film-forming inorganic compound is a polymer,
The plastic became the same plastic material as plasticized plastic water, and the retained water evaporated to become a foaming agent, which formed a foam without breaking the film formation. The specific gravity was 1 or less, typically 0.3 to 0.5. When the alkali metal content is high, ethylene glycol is used, and when the alkali metal content is low, polyethylene glycol is used.

【0029】本発明者等は,特開平8−73212号
で,防火木材の製法を提案した。然しながら,建築基準
法の外壁に使用できる準不燃木材を簡易には製造できな
かった。特許第2678345号の燐酸化合物を注入し
更にシリカゾルを注入する方法は,工法及び材料はコス
ト高となった。本発明のSi/Na比が2以上のPH1
2以下の固形分30%以上はアモルフアスで注入容易
で,800Kg/m注入し容易に準不燃試験に合格す
る成績を得た。その表面を前述アルコール80部と分子
量6000のポリエチレングリコール20部の混合液を
塗布浸透させて乾燥すると,2週間の強制溶脱試験で減
量は僅少で合格する成績を得た。
The present inventors have proposed a method for producing fire-resistant wood in Japanese Patent Application Laid-Open No. 8-73212. However, semi-incombustible wood that can be used for the outer walls of the Building Standards Law could not be easily manufactured. The method of injecting a phosphoric acid compound and further injecting silica sol disclosed in Japanese Patent No. 2678345 increased the cost of the method and materials. PH1 of the present invention having a Si / Na ratio of 2 or more
A solid content of 30% or more with a solid content of 2 or less was easily injected with an amorphous material, and 800 kg / m 3 was injected. When the surface was coated with a mixed solution of 80 parts of the alcohol and 20 parts of polyethylene glycol having a molecular weight of 6000, the mixture was permeated and dried.

【0030】[0030]

【作用と効果】高い成型生産性を有する合成樹脂を代替
し得る,水戻り性のない高分子量の水性造膜性無機化合
物を,Si/Na比を2以上,安定的には3以上とし,
PH12以下とすることにより可能となった。公知技術
では,水性無機化合物の重量平均分子量を4,000以
上にすることは困難であったが,濃縮し更に高分子量と
したことで,熱可塑性的な加熱脱水造膜硬化脱型が可能
となった。合成樹脂の汎用性は,ビーズやペレット化す
ることで自由な成型可能となった。水性無機化合物は硬
化しても水戻り性あって,ビーズ化しても付着性あり密
閉包装運搬性に難がった。水性無機物を脱水すれば加熱
しても可塑性を生じないから,保有水ある状態のビーズ
やペレット化をアルコキシド化して,表面を疎水化して
実現した。このビーズを使用し電子加熱すれば,3〜5
分の成型サイクルを生じ,極端には比重0.05の均一
発泡体が可能で,建材に適する0.2〜0.5の商業生
産が可能になった。無機と有機の繊維と複合すれば,未
硬化成型前駆物のSMCやBMCは勿論,シート生産も
可能となった。困難であった溶脱の僅少な外壁用準不燃
木材も可能になった。最も燃焼と廃棄物の公害物であっ
た発泡ポリスチレンやポリエステルFRPを代替し,本
発明品は破砕して投棄し土に還元する自然サイクル品と
なすことができた。
[Function and effect] A high molecular weight aqueous film-forming inorganic compound which can substitute for synthetic resin having high molding productivity and has no water return property, has a Si / Na ratio of 2 or more and stably 3 or more.
It became possible by setting the pH to 12 or less. According to the prior art, it was difficult to increase the weight average molecular weight of the aqueous inorganic compound to 4,000 or more. became. The general versatility of synthetic resins has been made possible by freely molding them into beads or pellets. The water-based inorganic compound has a water return property even when hardened, and has an adhesive property even when it is formed into beads, and has difficulty in hermetically packaging and transporting. Dehydration of an aqueous inorganic substance does not cause plasticity even when heated, so the surface was made hydrophobic by alkoxide-forming beads and pellets in the presence of water. If these beads are used for electronic heating, 3-5
A minute molding cycle has occurred, and in the extreme, a uniform foam having a specific gravity of 0.05 has become possible, and commercial production of 0.2 to 0.5 suitable for building materials has become possible. By combining with inorganic and organic fibers, it became possible to produce sheets as well as uncured molding precursors SMC and BMC. Semi-incombustible wood for exterior walls, which has been difficult to leaching, has become possible. By replacing expanded polystyrene and polyester FRP, which were the most pollutants of combustion and waste, the product of the present invention could be made into a natural cycle product that was crushed, dumped, and reduced to soil.

【作用効果を示す実施例】以下の実施例により作用効果
を示す。
Example showing the function and effect The function and effect will be shown by the following examples.

【0031】[0031]

【実施例−1】90〜99%純度の中国製金属シリコン
の塊状(5〜100mm)を,ステンレス製籠に大過剰
の150Kgを投入し,2mのステンレスタンクの低
部に設置し,1Tの水を投入し,次いで硼砂(USA,
Borax社製99%純度)50Kgと弗化ソーダ20
Kg(橋本化成製99%純度)を加え,更にPHが12
以下になるような苛性ソーダ70Kg(徳山ソーダ製)
を投入した。シリコン固体表面と低部に溶解した高濃度
アルカリ溶液反応で発熱し,沸騰する80度以上の温度
になった。数時間で沸騰は静まったが,夜間であっても
60度以上に維持するように自動調節し加温した。1昼
夜で,PH 11.9比重1.4の水溶液を得た。モル
比Si/Naは2.3以上であった。弗化ソーダと硼砂
の合計を,硼砂や亜硫酸ソーダ,亜燐酸塩,亜硝酸塩に
替えても,アルカリ金属をKOHやLiOHを使用して
も,アルカリ金属を反応液がPH12以下に保持するよ
うな配合にし,PHが12以下であれば,前記モル比は
2以上で,製品液体の流動性は,いずれの場合も500
CP以下であった。以後これらを総称してLCと略称す
る。前配合で硼砂を除き,苛性ソーダを150Kgに配
合しPHを12以上にした場合,反応し沸騰する時間は
長く,冷却をして鎮静化する必要があった。製品モル比
は,Si/Na=1.8以下で,PHが12〜12.
4,比重は1.4〜1.5であった。以後MFと仮称す
る。スライドガラスに塗り乾燥し1000倍にした顕微
鏡写真を観ると,前記LCは塗膜状であったが,MFは
コロイドであった。更に煮沸濃縮しても,MFはコロイ
ドが集結した形で塗膜状にはならなかった。の電子顕微
鏡写真を第4〜5図に示した。
Example -1] 90 to 99% purity of the Chinese metal silicon lumps of (5 to 100 mm), a large excess of 150Kg was charged into a stainless steel basket, placed in the lower part of the stainless steel tank 2m 3, 1T Of water and then borax (USA,
50 kg of Borax 99% purity) and sodium fluoride 20
Kg (99% purity, manufactured by Hashimoto Kasei).
70Kg of caustic soda (made by Tokuyama soda)
Was introduced. Heat was generated by the reaction of the high-concentration alkaline solution dissolved in the silicon solid surface and the lower part, and the temperature rose to 80 ° C or more. The boiling subsided in a few hours, but the temperature was automatically adjusted so as to maintain the temperature at 60 ° C or higher even at night, and heating was performed. One day and night, an aqueous solution having a PH of 11.9 and a specific gravity of 1.4 was obtained. The molar ratio Si / Na was 2.3 or more. Even if the total amount of sodium fluoride and borax is changed to borax, sodium sulfite, phosphite, or nitrite, or KOH or LiOH is used as the alkali metal, the reaction liquid can maintain the alkali metal at pH 12 or less. If the pH is 12 or less, the molar ratio is 2 or more, and the fluidity of the product liquid is 500 in each case.
It was below CP. Hereinafter, these are collectively abbreviated as LC. When the pH was adjusted to 12 or more by adding caustic soda to 150 kg and excluding borax in the previous formulation, the reaction and boiling time was long, and it was necessary to cool and calm down. The product molar ratio is Si / Na = 1.8 or less and PH is 12-12.
4, the specific gravity was 1.4 to 1.5. Hereinafter, this is temporarily referred to as MF. When viewed on a microscope photograph of a slide glass coated and dried at a magnification of 1000, the LC was in the form of a coating film, but the MF was a colloid. Even after boiling and concentration, MF did not form a coating film in the form of aggregated colloids. 4 and 5 are shown in FIGS.

【0032】[0032]

【実施例−2】前実施例の反応途中の保有水80%で比
重1.2,PH12.2のLC水溶液を加圧2K/cm
2容器中で120度に加熱した。比重1.5で,PHは
11.5になった。同比重の水ガラス1号品は水飴状に
高粘度化したが,LC製品は100〜300センチポイ
ズの流動性ある淡黄色液体であった。200度以上の加
熱温度は必要なかった。
Example 2 An aqueous LC solution having a specific gravity of 1.2 and a pH of 12.2 with 80% water retained during the reaction of the previous example was pressurized at 2 K / cm.
Heated to 120 degrees in two vessels. At a specific gravity of 1.5, the PH became 11.5. Water glass No. 1 product of the same specific gravity had a high viscosity like syrup, but the LC product was a light yellow liquid with a fluidity of 100 to 300 centipoise. No heating temperature above 200 degrees was required.

【0033】[0033]

【実施例−3】前実施例の保有水80%の半応途中液
を,佐久間製作所の減圧加熱装置で,1トール減圧80
度C加熱し,常圧130度相当加熱した。加圧加熱した
時と同様に,比重1.48,PH11.34の水溶液を
得た。保有水の大小に応じて加熱温度と速度を調節して
対応ができるので,保有水に左右されないで製造でき
る。加熱温度を増すと造粘して200度以上にはできな
かった。常圧150度C相当温度以上の必要はなかっ
た。
Example 3 The half-way liquid of 80% of the water retained in the previous example was decompressed to 1 Torr by a reduced pressure heating device of Sakuma Works.
C and heated to 130 ° C under normal pressure. An aqueous solution having a specific gravity of 1.48 and a pH of 11.34 was obtained in the same manner as when heating under pressure. Since the heating temperature and speed can be adjusted according to the size of the water holding, it can be manufactured without being affected by the water holding. When the heating temperature was increased, the viscosity was not increased to 200 ° C. or more. There was no need for the temperature to be equal to or higher than the normal pressure of 150 ° C.

【0034】[0034]

【実施例−4】加圧5K/cm2の20リットル容器中
に,水15Kgと金属シリコン5Kgを入れ,苛性カリ
1Kgと硼砂2Kgを同時投入し,130度に加熱し
た。小孔を設け排気したところ,反応が進行すれば,水
素を排出するので,それを確認するため排気に点火した
ところ火炎を生じた。モル比3の,PH11.2,比重
1.48のLC液を得た。
Example 4 In a 20 liter container with a pressure of 5 K / cm2, 15 kg of water and 5 kg of metallic silicon were charged, and 1 kg of caustic potash and 2 kg of borax were simultaneously charged and heated to 130 ° C. When the reaction proceeded, hydrogen was exhausted when a small hole was provided and exhausted. When the exhaust gas was ignited to confirm this, a flame was generated. An LC solution having a molar ratio of 3 and a pH of 11.2 and a specific gravity of 1.48 was obtained.

【0035】[0035]

【実施例−5】(実施例−1)と(実施例−4)のLC
製品と,公知フリットとの,元素分析値の比較を示す。
LCを加熱すると900度前後で,無機塗膜を形成し
た。
EXAMPLE-5 LC of (Example-1) and (Example-4)
4 shows a comparison of elemental analysis values between a product and a known frit.
When the LC was heated, an inorganic coating was formed at around 900 ° C.

【0036】[0036]

【実施例−6】SiO2/Al2O3=4のモル比を示
し層状化合物であるモンモリロナイトと,前記(実施例
−1)に示した PH11.9,比重1.4のLC液の
DTA−TG分析図を比較してみると,ほぼ相似した形
状を示した。前述LCのSi/Na=3のモル比物は,
含水はしても水に不溶性物になった。またLC液に35
%塩酸の5倍稀釈液を滴下しPHを観察するとPH10
までは直線下降するが,PH10で横這いになり,バッ
ハー帯がある。即ち,二珪酸板状の複層体であり,且つ
LCは層状に結合した高分子量を持った無機高分子と推
定される。
Example-6 DTA-TG analysis diagram of montmorillonite which is a layered compound showing a molar ratio of SiO2 / Al2O3 = 4 and LC solution of PH11.9 and specific gravity 1.4 shown in the above (Example-1) When they were compared, they showed almost similar shapes. The LC / Si / Na = 3 molar ratio is
Even if it contained water, it became insoluble in water. In addition, 35
A 5-fold diluted solution of 5% hydrochloric acid was dropped and the pH was observed.
Until it descends straight, it levels off at PH10 and has a Bacher band. That is, it is presumed that it is a disilicate plate-like multilayer body, and LC is an inorganic polymer having a high molecular weight bonded in layers.

【0037】[0037]

【実施例−7】
(実施例−1)のLCを日本化成分析
センターで,IRスペクトル分析した。 3800〜2400cm−1 シラノール吸着水 1000 cm−1 シロキサン吸着水 900 cm−1 シラノール 7 8 0 cm−1 シロキサン シラノールとシロキサンの存在と,200cp以下の低
粘性で,X線解析ではブロードででシャープなピークな
く非晶質である事を証明した。
Embodiment-7
The LC of (Example-1) was analyzed by IR spectrum at Nippon Kasei Analysis Center. 3800-2400cm-1 Silanol-adsorbed water 1000cm-1 Siloxane-adsorbed water 900cm-1 Silanol 780cm-1 Siloxane The presence of silanol and siloxane, low viscosity of 200cp or less, broad and sharp in X-ray analysis It proved to be amorphous without a peak.

【0038】[0038]

【実施例−8】硼酸・硼砂を含むLCは,オール化合物
である試薬ポリ,ジエチレンやポリプレングリコールと
任意に相溶した。炭酸グアニジン(三和化学製)とも相
溶した。ポリアミンエポキシ(ガンツ化成,荒川林産
製)液とも相溶した。
Example-8 The LC containing boric acid / borax was arbitrarily compatible with the reagents poly, diethylene and polypropylene glycol which were all compounds. It was also compatible with guanidine carbonate (manufactured by Sanwa Chemical). Also compatible with polyamine epoxy (Ganz Kasei, Arakawa Hayashi) solution.

【0039】[0039]

【実施例−9】上述モル比が2以上のLCは,500C
P以下の流動性あるので,綿・麻・毛・パルプ・木など
に含浸し,重量は被含浸材の2〜6倍になった。60〜
120度Cで発泡させずに乾燥し,保有水を20〜40
%にした。不織布であればSMCになり,短繊維であれ
ばBMCになった。原繊維の2倍以上の重量物の保有水
が20〜40%物であれば,リブ付き三次元形状の金型
にいれ,150度でプレス加熱した。その成型体は,肉
厚1mmでリブせいは10mmであったが,曲げ強度
は,200Kg/cm以上を生じた.補強材繊維はガ
ラスでも無機繊維でも有機繊維でも可能であるが,織布
よりも不織布がよく,例えば日清紡の綿ノーバインダー
不織布は加圧しても奇麗に成型できた。実施例−8のポ
リアミンやグアニジンハイブリッド物をシートに流し,
乾燥しフイルムを得た。
Embodiment-9 The above-mentioned LC having a molar ratio of 2 or more is 500 C
Since it has a fluidity of P or less, it was impregnated into cotton, hemp, wool, pulp, wood, etc., and the weight was 2 to 6 times that of the impregnated material. 60 ~
Dry at 120 ° C without foaming and keep the water at 20-40
%. The nonwoven fabric was SMC, and the short fiber was BMC. If the water content, which is twice or more the weight of the fibrous material, is 20 to 40%, it was placed in a rib-shaped three-dimensional mold and heated by pressing at 150 ° C. The molded product had a thickness of 1 mm and a rib thickness of 10 mm, but a bending strength of 200 kg / cm 2 or more. The reinforcing fiber can be glass, inorganic fiber or organic fiber, but a non-woven fabric is better than a woven fabric. For example, Nisshinbo's cotton non-binder non-woven fabric can be molded neatly under pressure. The polyamine or guanidine hybrid of Example-8 was poured on a sheet,
It was dried to obtain a film.

【0040】[0040]

【実施例−10】上述モル比2以上のLCを乾燥器で保
有水30%にまで乾燥し粒状のペレット成型した。これ
をシリコン型に投入し並べて,加圧成型した。これに蒸
気排出隙間を用意してあれば200度C加熱したとこ
ろ,厚み20mmX300mmX300mmの比重0.
4の発泡軽量体を成型できた。加熱可塑化発泡造膜硬化
成型できた例である。
Example 10 The above-mentioned LC having a molar ratio of 2 or more was dried in a drier to 30% of retained water, and formed into granular pellets. This was put into a silicon mold, arranged side by side, and pressed. If a steam discharge gap is prepared, heating at 200 ° C. results in a specific gravity of 20 mm × 300 mm × 300 mm.
4 was able to be molded. This is an example in which heat plasticization and foam film hardening and molding were performed.

【0041】[0041]

【実施例−11】山城精密機械の液状固化成型のリム試
験機で,モル比3の固形分30%LC液を減圧加熱し,
保有水を30%とし,特殊ヒーター付き金型で注入加熱
成型できた。液相から可塑化物となり固相化硬化したも
のである。製品は肉厚0.7mmの小型カップ状品であ
った。ヒーター付き金型の改良により,サイクルスピー
ドも大型製品の成型も可能な事が解った。ペレット化す
れば,三次元インジェクション成型も可能であることを
示した。30%溶液を濃縮すると,重量平均分子量は上
昇し,従って前述モル比は4以上となった。モル比が4
以上物ば,200度C以上の加熱硬化体は水に浸漬して
も不溶性になった。
Example 11: A 30% solids LC solution having a molar ratio of 3 was heated under reduced pressure using a liquid solidification molding rim tester of Yamashiro Precision Machinery.
Injection heating molding was possible with a mold equipped with a special heater, with the retained water at 30%. It becomes a plasticized product from a liquid phase and is solidified and cured. The product was a small cup with a thickness of 0.7 mm. It was found that improved molds with heaters enabled both cycle speed and molding of large products. It was shown that three-dimensional injection molding is possible if pelletized. Concentration of the 30% solution increased the weight average molecular weight, thus increasing the molar ratio to 4 or more. Molar ratio of 4
With the above materials, the heat-cured body at 200 ° C. or higher became insoluble even when immersed in water.

【0042】[0042]

【実施例−12】前述モル比3以上のLC30%液であ
っても,紙コップに30gとり,350Wの電子レンジ
に入れ,5分間加熱した。これを観察すると,沸騰蒸発
し濃縮され可塑化凝固物になり,次に発泡膨張し,水分
が消失して硬化固化した。ザラメ砂糖からカルメラ焼き
した時と同様な成型相を示した。熱源は,電気・電子・
音波などの加熱装置はいずれも使用可能である。300
度C加熱すると,水に不溶性物となった。
Example -12 Even with the above-mentioned LC 30% liquid having a molar ratio of 3 or more, 30 g of the liquid was placed in a paper cup, placed in a microwave oven of 350 W, and heated for 5 minutes. When this was observed, it was boiled off and concentrated to form a plasticized coagulated product, which then expanded and expanded, lost water and solidified. It showed the same molding phase as when carmela was baked from caramelized sugar. Heat sources are electric, electronic,
Any heating device such as a sound wave can be used. 300
After heating at a temperature of C, it became insoluble in water.

【0043】[0043]

【実施例−13】比重0.3の杉材 25X150X3
00(単位mm)を上記モル比2の比重1.4のLC液
に入れて,80度Cの煮沸した。約比重0.9となった
ので乾燥した(80度C48時間)ところ,比重0.5
4となり,固形分は240Kg/m残存した。これを
外壁用の2週間溶脱試験したが,その後の乾燥重量の減
量は5%以内であった。この板を12mm厚にし,22
cm角に接続し,準不燃防火試験した(東洋精機防火試
験機)。TDθは12で,残炎は0で準不燃合格品であ
った。
[Example-13] Cedar wood having a specific gravity of 0.3 25X150X3
00 (unit: mm) was placed in the above-mentioned LC solution having a molar ratio of 2 and a specific gravity of 1.4, and was boiled at 80 ° C. It was dried (80 ° C for 48 hours) because the specific gravity was about 0.9, and the specific gravity was 0.5.
The solid content was 240 kg / m 3 . This was subjected to a leaching test for the outer wall for 2 weeks, and the loss of dry weight thereafter was within 5%. Make this plate 12mm thick,
It was connected to a cm square and subjected to a quasi-noncombustible fire test (Toyo Seiki Fire Test Machine). The TDθ was 12, the afterflame was 0, and the product was a quasi-noncombustible product.

【0044】[0044]

【実施冷−14】前述LC液がPH12以下で Si/
Na比が2以上であれば,表面疎水化した粉体やビーズ
やペレット化する実施例を示す。2価アルコールの代表
例としてエチレングライコール(無水試薬)を,また多
価アルコールのポリエチレングリコールを,LC液に重
量比1%以上100%を混合すると,時間と共に造粘す
る。多価物では増量すれば短時間で凝集物となる。1価
アルコールを混合すればメチルは早くエチル,IPAと
凝集速度は遅くなる。最も凝集の早い低沸点のメタノー
ルに,または前述多価アルコール物例えばポリエチレン
グリコールを3〜20重量部を混合し、その中に,無添
加の,または前述1乃至多価物を1%以上混合したLC
液を,スプレーして散布すれば微細物になり,滴下すれ
ばビーズかペレット状成型物となり,引き上げて乾燥す
れば,表面疎水化した成型前駆物となった。型内で18
0度加熱すると発泡し融着した。300度以内の加熱し
成型できた。
[Execution cooling -14] When the above-mentioned LC liquid is PH12 or less, Si /
When the Na ratio is 2 or more, an example will be described in which powder, beads, or pellets whose surface is hydrophobized are formed. Mixing ethylene glycol (anhydrous reagent) as a typical example of a dihydric alcohol and polyethylene glycol of a polyhydric alcohol with an LC solution at a weight ratio of 1% or more and 100% viscous with time. In the case of multivalent materials, if the amount is increased, aggregates are formed in a short time. If a monohydric alcohol is mixed, methyl is faster in ethyl and IPA is slower in aggregation. 3 to 20 parts by weight of the above-mentioned polyhydric alcohol, for example, polyethylene glycol, is mixed with the low-boiling point methanol, which is the fastest flocculation, and 1% or more of the non-added or the above-mentioned 1 to polyvalent is mixed therein. LC
The liquid was sprayed and sprayed to give a fine product, dropped to form beads or pellets, and pulled up and dried to form a surface-hydrophobic molding precursor. 18 in the mold
When heated to 0 degrees, it foamed and fused. Heating and molding within 300 degrees were possible.

【0045】[0045]

【本発明の作用効果】既発明の,水性造膜性無機化合物
には,その硬化物に,水戻り性があった。本発明は,水
性であっても硬化物に耐水性を生じるように,SiO2
/Na2Oモル比を,2以上に,確実には3以上にし,
PHを12以下にし,加熱脱水し保有水を3.7%以下
になせば耐水硬化体となった。合成樹脂のような熱可塑
性成型や発泡成型は,造膜成型をなし得る高分子量がな
ければ成型できない。水性物に高分子量があれば,加熱
脱水するに従い,可塑化物となるが,合成樹脂が加熱軟
化溶融する現象に近似した状態になり,加熱脱水硬化す
るに至る。本発明物は,シラノールやシロキサンの混合
物であるので,重量平均分子量で判断するのが相当であ
り,最低分子量が1000以上の有機高分子と同様な無
機高分子量を保持したことにより可能となった。前記粉
体前駆物は,加圧型内熱プレスで不燃無機絶縁物を成型
でき,ビーズやペレットを1〜10分サイクルで大型・
小型インジェクション成型することも可能になった。同
様に発泡体の成型も可能になった。現に,燃焼や廃棄公
害の主原因となっている,合成樹脂,特に発泡スチロー
ルやポリエステル製品のFRPを,不燃無機物代替生産
しうることになった。
[Effects of the present invention] The aqueous film-forming inorganic compound of the present invention has a water return property in its cured product. The present invention is directed to a method of producing a cured product having water resistance even if it is aqueous.
/ Na2O molar ratio is 2 or more, surely 3 or more,
When the pH was adjusted to 12 or less and the water content was reduced to 3.7% or less by heating and dehydration, a water-resistant cured product was obtained. Thermoplastic molding or foam molding such as synthetic resin cannot be molded without a high molecular weight capable of forming a film. If the aqueous material has a high molecular weight, it becomes a plasticized product as it is heated and dehydrated. However, the synthetic resin is in a state similar to a phenomenon in which the synthetic resin is softened and melted by heating, leading to heat dehydration and hardening. Since the product of the present invention is a mixture of silanol and siloxane, it is appropriate to judge by the weight average molecular weight, and it became possible by maintaining the same inorganic high molecular weight as the organic high molecular weight of 1000 or more. . The powder precursor can be molded into a non-combustible inorganic insulator by a pressurized internal heat press.
Small injection molding is now possible. Similarly, molding of foams became possible. In fact, it has become possible to produce non-combustible inorganic substances for synthetic resin, especially FRP of styrene foam and polyester products, which is the main cause of combustion and waste pollution.

【0046】[0046]

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

図−1は,前述LC液を塗布した直後のFTIR分析を
示す。図−2は,図−1物を常温放置したところ,左端
水酸基ピークの高さが減少した。これは常温で造膜して
いた事実を証している。図−3は,前発明品のSEM写
真で,水に分散したコロイドであることを示した。図−
4は,これを濃縮しても,水が蒸発しコロイドは近接し
ているが,均一塗膜化しない状態を示した。図−5は,
本発明のSi/Naが2以上でPH12以下の場合のS
EM写真である。コロイドの姿なく合成樹脂のような高
分子塗膜状になったことを示した。
FIG. 1 shows an FTIR analysis immediately after the application of the above-mentioned LC solution. In FIG. 2, the height of the leftmost hydroxyl group peak decreased when the product of FIG. 1 was left at room temperature. This proves that the film was formed at room temperature. FIG. 3 is an SEM photograph of the product of the invention, showing that it is a colloid dispersed in water. Figure-
No. 4 shows a state in which water is evaporated and the colloids are close to each other, but the film is not formed into a uniform film even when the solution is concentrated. Figure 5 shows
S of the present invention when Si / Na is 2 or more and PH is 12 or less
It is an EM photograph. It showed that it became a polymer coating like synthetic resin without the appearance of colloid.

───────────────────────────────────────────────────── フロントページの続き Fターム(参考) 4G073 BA04 BA56 BA63 BB57 BB59 BD03 BD11 BD18 BD26 CM29 CN03 CN09 FC18 FC22 FC25 FC26 GA01 GA27 UA08 4G075 AA23 AA24 BB02 CA02  ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G073 BA04 BA56 BA63 BB57 BB59 BD03 BD11 BD18 BD26 CM29 CN03 CN09 FC18 FC22 FC25 FC26 GA01 GA27 UA08 4G075 AA23 AA24 BB02 CA02

Claims (9)

【特許請求の範囲】[Claims] 【請求項1】 200度C以下80度C以上の相当温度
範囲内で,水性造膜性無機化合物生成能ある配合材を,
Si/Na比を2以上の成分比に,反応し形成した,保
有水が80重量部以内である,重量平均分子量1000
以上の高分子量水性造膜性無機化合物を成型前駆物とな
し,加熱し可塑物となし脱水硬化成型する方法。
1. An aqueous film-forming inorganic compound-forming compound having a temperature range of 200 ° C. or lower and 80 ° C. or higher,
The water content is less than 80 parts by weight, the weight average molecular weight is 1000, which is formed by reacting the Si / Na ratio to the component ratio of 2 or more.
A method in which the above-mentioned high molecular weight aqueous film-forming inorganic compound is used as a molding precursor, heated to be a plastic, and dehydrated and cured.
【請求項2】 請求項1項の成型前駆物は,前記水性造
膜性無機化合物生成能ある配合材か,または前記反応し
形成した材を,前項記載温度範囲内で加圧または減圧下
高温反応で形成した,保有水が80重量部以内である高
分子量水性造膜性無機化合物
2. The molding precursor according to claim 1, wherein the compounded material capable of forming an aqueous film-forming inorganic compound or the material formed by the reaction is heated to a high temperature under pressure or reduced pressure within the temperature range described in the preceding item. High-molecular-weight aqueous film-forming inorganic compound formed by the reaction and containing less than 80 parts by weight of water
【請求項3】 請求項1〜2の前記高分子量水性造膜性
無機化合物が,シロキサンとシラノール塩からなり,S
i/Na比が2以上であり,アモルフアス状でPHが1
2以下で,500CP以下の低粘性の高分子量水性造膜
性無機化合物
3. The high-molecular-weight aqueous film-forming inorganic compound according to claim 1, comprising a siloxane and a silanol salt.
i / Na ratio is 2 or more, PH is 1
Low viscosity, high molecular weight aqueous film-forming inorganic compound with a viscosity of 2 or less and 500 CP or less
【請求項4】 請求項1〜3の前記高分子量水性造膜性
無機化合物が,硼酸か硼砂を含み釉薬に近似した成分と
し,アモルフアス状でPH12以下である高分子量水性
造膜性無機化合物
4. The high-molecular-weight aqueous film-forming inorganic compound according to claim 1, wherein the high-molecular-weight aqueous film-forming inorganic compound contains boric acid or borax and is a component similar to a glaze, and is amorphous and has a pH of 12 or less.
【請求項5】 請求項1〜4の前記高分子量水性造膜性
無機化合物を,1価または多価/1価と多価を混合した
ヒドロキシオール化合物と混合し,または飛散か滴下か
切断落下し前記ヒドロキシオール化合物と接触反応せし
めて,アルコキシド化合物となした高分子量水性造膜性
無機化合物
5. The high molecular weight aqueous film-forming inorganic compound according to claim 1, which is mixed with a monovalent or polyvalent / monovalent / polyvalent mixed hydroxyol compound, or scattered, dropped or cut and dropped. A high molecular weight aqueous film-forming inorganic compound which has been brought into contact with the hydroxyol compound to form an alkoxide compound.
【請求項6】請求項1〜5の前記高分子量水性造膜性無
機化合物の保有水分が40重量部以下であり,綿糸や
麻,カーボン繊維,ガラス繊維などの有機や無機繊維を
混合しまたは混合しない,濃縮物やフイルム,ペレッ
ト,シート,SMC,BMCとなし,加熱脱水硬化成型
する加熱成型前駆物や加熱発泡硬化成型前駆物となし
た,高分子量水性造膜性無機化合物
6. The high-molecular-weight aqueous film-forming inorganic compound according to claim 1, wherein the water content of the high-molecular-weight aqueous film-forming inorganic compound is 40 parts by weight or less, and an organic or inorganic fiber such as cotton thread, hemp, carbon fiber, or glass fiber is mixed. A high molecular weight aqueous film-forming inorganic compound that is not mixed, has no concentrates, films, pellets, sheets, SMCs, and BMCs, and has become a heat molding precursor or a heat foaming curing molding precursor for heat dehydration curing.
【請求項7】請求項1〜6の前記高分子量水性造膜性無
機化合物を,150度C以上に加熱して,可塑化し保有
水を30重量部以下に脱水し,硬化体となすことができ
る,高分子量水性造膜性無機化合物成形前駆物と,それ
を常圧か加圧下で,及び注型か加圧注型し,加熱硬化す
る成型法
7. The method according to claim 1, wherein the high molecular weight aqueous film-forming inorganic compound according to claim 1 is heated to 150 ° C. or more to plasticize and dehydrate the retained water to 30 parts by weight or less to form a cured product. A high molecular weight aqueous film-forming inorganic compound forming precursor that can be formed, and a molding method in which it is heated and cured at normal pressure or under pressure, and cast or pressed under pressure
【請求項8】請求項1〜7の前記高分子量水性造膜性無
機化合物成型前駆物を,保有水を発泡剤となし,150
度C以上300度C以下に加熱し硬化して比重1以下の
発泡体になした無機軽量物と,前記高分子量水性造膜性
無機化合物成型前駆物を注型して,常圧または加圧加熱
し軽量硬化物とする成型法
8. A method according to claim 1, wherein said high-molecular-weight aqueous film-forming inorganic compound molding precursor is prepared by using water as a foaming agent.
An inorganic lightweight material which has been heated and cured to a temperature of not less than 300 ° C. to form a foam having a specific gravity of 1 or less, and the high molecular weight aqueous film-forming inorganic compound molding precursor, are cast at normal pressure or pressure. Molding method to make lightweight cured product by heating
【請求項9】請求項1〜5項の,高分子量熱可塑性水性
造膜性無機化合物を,煮沸含浸か加圧または減圧圧入し
て,130度以下で乾燥して,含水率を10%以下にし
た溶脱微量の防火木材とその成型法
9. A high-molecular-weight thermoplastic aqueous film-forming inorganic compound according to claim 1, which is dried by impregnation at 130 ° C. or less by boiling impregnation or pressurization or press-in under reduced pressure to reduce the water content to 10% or less. Trace leached wood for fire protection and its molding method
JP27289799A 1999-08-22 1999-08-22 High molecular weight aqueous film-forming inorganic compound molding precursor and molding method thereof Expired - Fee Related JP4291468B2 (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003000806A2 (en) * 2001-06-22 2003-01-03 Hiroshi Kokuta Aqueous film forming inorganic composition, inorganic foam, thermally insulating composite and method for production thereof
JP2008307485A (en) * 2007-06-15 2008-12-25 Hiroshi Kokuta Method of controlling colloid particle diameter in water based film forming inorganic colloid solution
JP2013082586A (en) * 2011-10-11 2013-05-09 Saibun Hayashi Modifier production apparatus and modifier

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0714801B2 (en) * 1988-06-10 1995-02-22 株式会社コーミックス Method for producing aqueous film-forming inorganic compound
JPH0873212A (en) * 1994-07-07 1996-03-19 Koomitsukusu:Kk High concentration boric acid compound and composition for fireproofing/fire resisting use containing the same and binding material and fireproof/fire resistant material using the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0714801B2 (en) * 1988-06-10 1995-02-22 株式会社コーミックス Method for producing aqueous film-forming inorganic compound
JPH0873212A (en) * 1994-07-07 1996-03-19 Koomitsukusu:Kk High concentration boric acid compound and composition for fireproofing/fire resisting use containing the same and binding material and fireproof/fire resistant material using the same

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003000806A2 (en) * 2001-06-22 2003-01-03 Hiroshi Kokuta Aqueous film forming inorganic composition, inorganic foam, thermally insulating composite and method for production thereof
WO2003000806A3 (en) * 2001-06-22 2003-03-13 Hiroshi Kokuta Aqueous film forming inorganic composition, inorganic foam, thermally insulating composite and method for production thereof
JPWO2003000806A1 (en) * 2001-06-22 2004-10-07 博 穀田 Aqueous film-forming inorganic composition, inorganic foam, heat-insulating composite, and methods for producing them
JP2008307485A (en) * 2007-06-15 2008-12-25 Hiroshi Kokuta Method of controlling colloid particle diameter in water based film forming inorganic colloid solution
JP2013082586A (en) * 2011-10-11 2013-05-09 Saibun Hayashi Modifier production apparatus and modifier

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