JPH11156838A - Production of cured inorganic material - Google Patents

Production of cured inorganic material

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Publication number
JPH11156838A
JPH11156838A JP32672597A JP32672597A JPH11156838A JP H11156838 A JPH11156838 A JP H11156838A JP 32672597 A JP32672597 A JP 32672597A JP 32672597 A JP32672597 A JP 32672597A JP H11156838 A JPH11156838 A JP H11156838A
Authority
JP
Japan
Prior art keywords
cured
inorganic
cured product
water
mold
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.)
Pending
Application number
JP32672597A
Other languages
Japanese (ja)
Inventor
Katsuzo Nitta
勝三 新田
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.)
Sekisui Chemical Co Ltd
Original Assignee
Sekisui Chemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sekisui Chemical Co Ltd filed Critical Sekisui Chemical Co Ltd
Priority to JP32672597A priority Critical patent/JPH11156838A/en
Publication of JPH11156838A publication Critical patent/JPH11156838A/en
Pending legal-status Critical Current

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  • Devices For Post-Treatments, Processing, Supply, Discharge, And Other Processes (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain a cured inorganic material excellent in surface appearance, durability, and weatherability by a method in which a prescribed curable inorganic composition is mixed, molded into a plate, and cured by a dehydrating polycondensation reaction, and generated excess water is removed preferentially from the back side of the cured material. SOLUTION: A curable inorganic composition composed of reactive inorganic fine particles A of SiO2 -Al2 O3 system, an alkali metal silicate B, and water C is kneaded by a mixer 2, cast into a molding mold 1, and heated with the mold 1 in a heating furnace 5 to be cured by a dehydrating polycondensation reaction. After that, the cured composition is dried in a drying furnace 6, and generated excess water is removed preferentially from the back side of the cured composition to produce a cured inorganic material. In this way, soluble components such as unreacted silicate ions are transferred to the back side of the cured material, and even when the cured material absorbed water thereafter, the generation of change in appearance associated with a chemical change on the surface side is prevented.

Description

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

【０００１】[0001]

【発明の属する技術分野】本発明は、無機質硬化体の製
造方法に関するものであり、より詳しくは、耐水性・耐
候性に優れた高耐久性の無機質硬化体を得られるように
した無機質硬化体の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a cured inorganic material, and more particularly, to a cured inorganic material having high durability and excellent water resistance and weather resistance. And a method for producing the same.

【０００２】[0002]

【従来の技術】建築物の外壁や屋根などに用いられる無
機質硬化体のパネルの製造方法には、従来、特公平６−
１５４２８号公報に記載されたようなものがある。2. Description of the Related Art A method of manufacturing a panel of an inorganic cured material used for an outer wall or a roof of a building has conventionally been disclosed in Japanese Patent Publication No.
There is one such as described in JP-A-15428.

【０００３】上記公報に記載された無機質硬化体の製造
方法では、要するに、アルカリ金属珪酸塩の水溶液やＳ
ｉＯ2−Ａｌ2Ｏ3系反応性無機質粉体を含む硬化性無機
質組成物に発泡剤を加えてバッチミキサーなどで混合・
混練し、得られた混練物を所定の雌型に注入すると共に
雌型に雄型を嵌合装着し、型内に混練物を発泡充填させ
た後、型ごと熱エネルギーを付与し脱水縮重合反応を起
こさせて硬化させ、得られた硬化体を脱型して乾燥させ
ることにより、最終的に無機質硬化体を得るようにして
いる。[0003] In the method for producing an inorganic cured product described in the above-mentioned publication, in short, an aqueous solution of alkali metal silicate or S
A foaming agent is added to the curable inorganic composition containing the iO 2 -Al 2 O 3 -based reactive inorganic powder and mixed with a batch mixer or the like.
After kneading, the obtained kneaded material is poured into a predetermined female mold, a male mold is fitted and mounted on the female mold, and the kneaded material is foam-filled in the mold. A reaction is caused to cure, and the obtained cured product is removed from the mold and dried to finally obtain an inorganic cured product.

【０００４】[0004]

【発明が解決しようとする課題】しかしながら、上記従
来の無機質硬化体の製造方法には、以下のような問題が
あった。However, the above-mentioned conventional method for producing an inorganic cured product has the following problems.

【０００５】即ち、硬化性無機質組成物の硬化体は、硬
化終了後も未反応の珪酸イオン、アルカリ金属イオンな
どの可溶成分が内部に存在し、硬化後の乾燥段階で表面
からの水の蒸発に伴い、これらの可溶成分が硬化体の表
面へと移動するため、硬化体表面に非常に薄い可溶成分
の層が形成されることとなるが、製造後に行われる耐水
試験や、耐候試験などで無機質硬化体が吸水した際に、
上記可溶成分によって表面に化学的変化を伴う外観変化
を生じることがあった。That is, in the cured product of the curable inorganic composition, soluble components such as silicate ions and alkali metal ions which are not reacted even after the completion of the curing are present inside, and water from the surface is dried at the drying stage after the curing. Due to the evaporation of these soluble components to the surface of the cured product due to evaporation, a very thin layer of the soluble component is formed on the surface of the cured product. When the inorganic cured body absorbs water in tests etc.,
In some cases, the soluble component causes a change in the appearance of the surface accompanied by a chemical change.

【０００６】そこで、本発明は、上述の実情に鑑み、外
観変化を生じうる可能性のある層が無機質硬化体の裏面
側にくるようにして、表面側外観に優れ、かつ耐水性・
耐候性に優れた高耐久性の無機質硬化体を得られるよう
にした無機質硬化体の製造方法を提供することを目的と
するものである。Therefore, in view of the above-mentioned circumstances, the present invention is designed such that a layer which may cause a change in appearance is located on the back side of the inorganic cured product, so that the appearance on the front side is excellent and water resistance and water resistance are improved.
It is an object of the present invention to provide a method for producing an inorganic cured product that can obtain a highly durable inorganic cured product having excellent weather resistance.

【０００７】[0007]

【課題を解決するための手段】本発明は、ＳｉＯ2−Ａ
ｌ2Ｏ3系反応性無機質粉体、アルカリ金属珪酸塩、水か
らなる硬化性無機質組成物を混合し、板状に成形し、脱
水縮重合反応を起こさせて硬化させた後、発生する余剰
水分を硬化体の裏面側から先に除去し、無機質硬化体を
製造することを特徴とする無機質硬化体の製造方法にか
かるものである。According to the present invention, there is provided an SiO 2 -A
l 2 O 3 system reactive inorganic powder, alkali metal silicates, mixed-setting inorganic composition consisting of water, then molded into a plate, after curing by causing a dehydration condensation polymerization reaction, to generate excess The present invention relates to a method for producing an inorganic cured product, which comprises removing water from the back side of the cured product first to produce an inorganic cured product.

【０００８】この場合において、混練物に含有される水
のうち２０％以上を硬化体の裏面側から先に除去するよ
うにしても良い。In this case, 20% or more of the water contained in the kneaded material may be removed first from the back side of the cured product.

【０００９】また、脱型に際し、前記硬化体の裏面側型
枠を除去し、所定量の水が蒸発した後、表面側型枠を除
去するようにしても良い。[0009] Further, at the time of demolding, the back side mold of the cured product may be removed, and after a predetermined amount of water evaporates, the front side mold may be removed.

【００１０】上記手段によれば、以下のような作用が得
られる。According to the above means, the following effects can be obtained.

【００１１】ＳｉＯ2−Ａｌ2Ｏ3系反応性無機質粉体
（Ａ）、アルカリ金属珪酸塩（Ｂ）、水（Ｃ）からなる
硬化性無機質組成物を混合し、板状に成形し、脱水縮重
合反応を起こさせて硬化させた後、発生する余剰水分を
硬化体の裏面側から先に除去し、特に、混練物に含有さ
れる水のうち２０％以上を硬化体の裏面側から先に除去
し、無機質硬化体を製造するようにしたので、未反応の
珪酸イオンなどの可溶成分が硬化体の裏面側へ移動する
こととなり、その後に無機質硬化体が吸水した場合で
も、表面側に化学的変化を伴う外観変化を生じることが
防止される。A curable inorganic composition comprising a SiO 2 —Al 2 O 3 -based reactive inorganic powder (A), an alkali metal silicate (B) and water (C) is mixed, formed into a plate, and dehydrated. After the condensation polymerization reaction is caused to cure, excess water generated is first removed from the back side of the cured body, and in particular, 20% or more of the water contained in the kneaded material is removed from the back side of the cured body. In order to produce an inorganic cured product, soluble components such as unreacted silicate ions move to the back side of the cured product, and even if the inorganic cured product subsequently absorbs water, The appearance change accompanying the chemical change is prevented.

【００１２】これにより、表面側外観に優れ、かつ耐水
性・耐候性に優れた高耐久性の無機質硬化体を得ること
ができるようになる。As a result, it is possible to obtain a highly durable inorganic cured body having excellent surface appearance and excellent water resistance and weather resistance.

【００１３】[0013]

【発明の実施の形態】以下、本発明の実施の形態を、図
示例と共に説明する。Embodiments of the present invention will be described below with reference to the drawings.

【００１４】図１は、本発明の第一の実施の形態であ
る。FIG. 1 shows a first embodiment of the present invention.

【００１５】本発明は、ＳｉＯ2−Ａｌ2Ｏ3系反応性無
機質粉体（Ａ）、アルカリ金属珪酸塩（Ｂ）、水（Ｃ）
からなる硬化性無機質組成物を混合・混練し、この混練
物を成形用型１内に注型し、混練物を成形用型１ごと加
熱し脱水縮重合反応を起こさせて硬化させた後、発生す
る余剰水分を硬化体の裏面側から先に除去し、無機質硬
化体を製造するようにしたところにその特徴がある。The present invention is directed to a SiO 2 -Al 2 O 3 -based reactive inorganic powder (A), an alkali metal silicate (B), and water (C).
After mixing and kneading the curable inorganic composition consisting of: casting the kneaded material into the molding die 1, and heating the kneaded material together with the molding die 1 to cause a dehydration-condensation polymerization reaction and curing, The feature is that excess moisture generated is removed first from the back side of the cured product to produce an inorganic cured product.

【００１６】特に、混練物に含有される水のうち２０％
以上を硬化体の裏面側から先に除去するようにしたとこ
ろにその特徴がある。In particular, 20% of the water contained in the kneaded material
The feature is that the above is removed first from the back side of the cured body.

【００１７】さらに、脱型に際し、前記硬化体の裏面側
型枠を除去し、所定量の水が蒸発した後、表面側型枠を
除去するようにしたところにその特徴がある。Further, when the mold is removed, the back side mold of the cured product is removed, and after a predetermined amount of water evaporates, the front side mold is removed.

【００１８】以下に、上記をより詳細に説明する。Hereinafter, the above will be described in more detail.

【００１９】先ず、図１に示すように、ＳｉＯ2−Ａｌ2
Ｏ3系反応性無機質粉体（Ａ）と、アルカリ金属珪酸塩
（Ｂ）の水溶液などから成る原料を用意する。[0019] First, as shown in FIG. 1, SiO 2 -Al 2
A raw material comprising an O 3 -based reactive inorganic powder (A) and an aqueous solution of an alkali metal silicate (B) is prepared.

【００２０】ＳｉＯ2−Ａｌ2Ｏ3系反応性無機質粉体
（Ａ）としては、ＳｉＯ2が、１０〜９０重量％、Ａｌ2
Ｏ3が、９０〜１０重量％のものが好ましく使用され
る。このような粉体としては、例えば、（Ａ１）粒径が
２０μｍ以下の粉体を８０重量％以上含有するフライア
ッシュ、（Ａ２）４００〜１０００Ｃ゜で焼成された粒
径が２０μｍ以下の粉体を８０重量％以上含有するフラ
イアッシュ、（Ａ３）フライアッシュ又は粘土を溶融し
気体中で噴霧することによって得られた無機質粉体、
（Ａ４）粘土に０．１〜３０ｋｗｈ／ｋｇの機械的エネ
ルギーを作用させることにより得られた無機質粉体、
（Ａ５）アルミナ系研磨材を製造する際のダスト、粉砕
焼成ボーキサイト等、（Ａ４）の無機質粉体を更に１０
０〜７５０Ｃ゜で加熱することにより得られた無機質粉
体、（Ａ６）メタカオリン、によりなる群より選ばれる
１種以上の無機質粉体等が使用できる。尚、組成と粒度
が適当であればこれらに限定される物ではない。Examples of the SiO 2 -Al 2 O 3 -based reactive inorganic powder (A), SiO 2 is 10 to 90 wt%, Al 2
O 3 is, those 90 to 10 wt% is preferably used. Examples of such powder include (A1) fly ash containing 80% by weight or more of powder having a particle size of 20 μm or less, and (A2) powder having a particle size of 20 μm or less fired at 400 to 1000 ° C. Ash, (A3) an inorganic powder obtained by melting fly ash or clay and spraying it in a gas;
(A4) an inorganic powder obtained by applying mechanical energy of 0.1 to 30 kwh / kg to clay;
(A5) An inorganic powder of (A4) such as dust and pulverized and fired bauxite at the time of producing an alumina-based abrasive is further
One or more inorganic powders selected from the group consisting of inorganic powders obtained by heating at 0 to 750 ° C and (A6) metakaolin can be used. The composition and particle size are not limited to these as long as they are appropriate.

【００２１】また、これらの粉体をそのまま用いてもよ
いが、活性化させるために、溶射処理、粉砕分級、機械
的エネルギーを作用させてもよい。Further, these powders may be used as they are, but in order to activate them, thermal spraying treatment, pulverization classification and mechanical energy may be applied.

【００２２】溶射処理によって粉体を活性化する方法と
しては、セラミックコーティングに適用される溶射技術
が応用される。その溶射技術は、好ましくは材料粉末が
２０００〜１６０００℃の温度で溶融され、３０〜８０
０ｍ／秒の速度で噴霧されるものであり、プラズマ溶射
法、高エネルギーガス溶射法、アーク溶射法等が可能で
ある。得られた粉体の比表面積は、０．１〜１００ｍ2
／ｇ が好ましい。As a method of activating powder by thermal spraying, a thermal spraying technique applied to ceramic coating is applied. The spraying technique is preferably such that the material powder is melted at a temperature of
It is sprayed at a speed of 0 m / sec, and a plasma spraying method, a high energy gas spraying method, an arc spraying method, or the like is possible. The specific surface area of the obtained powder is 0.1 to 100 m 2.
/ G is preferred.

【００２３】分級、粉砕によって粉体を活性化する方法
としては、従来公知の任意の方法が採用され、篩、比
重、風力、湿式沈降等による分級、ジェットミル、ロー
ルミル、ボールミルによる粉砕などがあげられる。これ
らの手段は併用されてもよい。As a method for activating the powder by classification and pulverization, any conventionally known method is adopted, and classification by a sieve, specific gravity, wind power, wet sedimentation, etc., pulverization by a jet mill, a roll mill, a ball mill and the like are mentioned. Can be These means may be used in combination.

【００２４】機械的エネルギーを作用させて粉体を活性
化する方法としては、ボール媒体ミル、媒体撹拌型ミ
ル、ローラミル等が使用され、作用させる機械的エネル
ギーとしては０．５ｋｗｈ／ｋｇ〜３０ｋｗｈ／ｋｇが
好ましい。小さいと粉体を活性化しにくく、大きいと装
置への負荷が大きい。As a method for activating the powder by applying mechanical energy, a ball medium mill, a medium stirring type mill, a roller mill or the like is used. The mechanical energy to be applied is 0.5 kWh / kg to 30 kWh / kg is preferred. If the particle size is small, it is difficult to activate the powder, and if the particle size is large, the load on the device is large.

【００２５】上記フライアッシュは、必要に応じて、焼
成されたものでもよい。焼成温度は、低いとフライアッ
シュの黒色が残って着色が困難となり、高いと、アルカ
リ金属珪酸塩（Ｂ）との反応性が低くなるので、４００
℃〜１０００℃であることが好ましい。The fly ash may be fired if necessary. If the firing temperature is low, the fly ash remains black and coloring becomes difficult, and if the firing temperature is high, the reactivity with the alkali metal silicate (B) becomes low.
It is preferable that the temperature is in the range of from 1000C to 1000C.

【００２６】本発明で用いられるアルカリ金属珪酸塩
（Ｂ）とは、Ｍ2Ｏ・ｎＳｉＯ2（Ｍ＝Ｌｉ、Ｋ、Ｎａま
たはそれらの混合物、）で表され、ｎ＝０．１〜８のも
のが好ましく、ｎ＝０．５〜３のものが好ましく、ｎ＝
０．５〜２．５のものが特に好ましい。すなわち、ｎが
０．１に満たない場合には、緻密な硬化体が得られず、
得られた硬化体の機械的強度が低くなる。The alkali metal silicate (B) used in the present invention is represented by M 2 O · nSiO 2 (M = Li, K, Na or a mixture thereof). Are preferably used, n = 0.5 to 3 are preferable, and n =
Those having a value of 0.5 to 2.5 are particularly preferred. That is, when n is less than 0.1, a dense cured body cannot be obtained,
The mechanical strength of the obtained cured product decreases.

【００２７】また、ｎが８を越えた場合、アルカリ金属
珪酸塩（Ｂ）水溶液がゲル化をおこしやすく粘度が急激
に上昇するため、粉体との混合が困難になるおそれがあ
る。If n exceeds 8, the alkali metal silicate (B) aqueous solution easily gels and the viscosity rises rapidly, which may make mixing with the powder difficult.

【００２８】アルカリ金属珪酸塩（Ｂ）は、ＳｉＯ2−
Ａｌ2Ｏ3系の反応性無機質粉体（Ａ）１００重量部に対
して０．２〜４５０重量部添加する必要があるが、好ま
しい添加量は、１０〜３５０重量部、さらに好ましい添
加量は２０〜２５０重量部である。The alkali metal silicate (B) is SiO 2-
It is necessary to add 0.2 to 450 parts by weight based on 100 parts by weight of the Al 2 O 3 -based reactive inorganic powder (A), but the preferred addition amount is 10 to 350 parts by weight, and the more preferred addition amount is 20 to 250 parts by weight.

【００２９】添加量が０．２重量部未満の場合には、反
応に必要なアルカリの量が少なすぎるために、硬化不良
となり、逆に、４５０重量部を越える場合には、硬化剤
（Ｄ）が多量となるため、無機質硬化体の耐水性に問題
が生じる。If the amount is less than 0.2 parts by weight, the amount of alkali required for the reaction is too small, resulting in poor curing. If the amount exceeds 450 parts by weight, the curing agent (D ) Becomes large, which causes a problem in water resistance of the inorganic cured product.

【００３０】本発明で使用される水（Ｃ）は上記アルカ
リ金属珪酸塩（Ｂ）の水溶液として添加されてもよい
し、独立して添加されてもよい。水（Ｃ）の量は、少な
くなると、十分に硬化せずまた混合が困難となり、多く
なると硬化体の強度が低下しやすくなるので上記反応性
無機質粉体（Ａ）１００重量部に対して、３５〜１５０
０重量部に限定され、好ましくは４５〜１０００重量
部、さらに好ましくは５０〜５００重量部である。添加
量が１０重量部を下回ると、反応性無機質粉体（Ａ）と
混合することが不可能となり、逆に、１０００重量部を
越えると、得られる無機質硬化体の機械的強度が低下す
る。The water (C) used in the present invention may be added as an aqueous solution of the alkali metal silicate (B) or may be added independently. If the amount of water (C) is too small, it will not be sufficiently cured and it will be difficult to mix, and if it is too large, the strength of the cured product tends to decrease, so 100 parts by weight of the reactive inorganic powder (A) 35-150
It is limited to 0 parts by weight, preferably 45 to 1000 parts by weight, more preferably 50 to 500 parts by weight. If the addition amount is less than 10 parts by weight, it becomes impossible to mix with the reactive inorganic powder (A). Conversely, if it exceeds 1000 parts by weight, the mechanical strength of the obtained cured inorganic material decreases.

【００３１】本発明においては、必要に応じて、硬化剤
（Ｄ）、発泡剤（Ｅ）、無機質充填材（Ｆ）、補強繊維
（Ｇ）、発泡助剤（Ｈ）、有機質発泡体もしくは無機質
発泡体などの発泡体（Ｉ）をさらに添加するようにして
もよい。In the present invention, if necessary, a curing agent (D), a foaming agent (E), an inorganic filler (F), a reinforcing fiber (G), a foaming aid (H), an organic foam or an inorganic foam A foam (I) such as a foam may be further added.

【００３２】硬化剤（Ｄ）としては、塩化マグネシウ
ム、酸化亜鉛などが挙げられる。Examples of the curing agent (D) include magnesium chloride and zinc oxide.

【００３３】硬化剤（Ｄ）としての塩化マグネシウム
は、ＭｇＣｌ2で表され、無水物、６水和物、１２水和
物が使用される。Magnesium chloride as the curing agent (D) is represented by MgCl 2 , and anhydrous, hexahydrate and dodecahydrate are used.

【００３４】塩化マグネシウムの添加量は、反応性無機
質粉体（Ａ）１００重量部に対して、１〜１００重量部
である必要がある。The amount of magnesium chloride added must be 1 to 100 parts by weight based on 100 parts by weight of the reactive inorganic powder (A).

【００３５】また、硬化剤（Ｄ）として酸化亜鉛を使用
する場合の添加量は、反応性無機質粉体（Ａ）１００重
量部に対して、１〜１００重量部である必要がある。When zinc oxide is used as the curing agent (D), the amount of addition must be 1 to 100 parts by weight based on 100 parts by weight of the reactive inorganic powder (A).

【００３６】添加量が１重量部を下回ると、無機質硬化
体の耐久性が悪くなり、逆に、１００重量部を越える
と、無機質硬化体の機械的強度が低下する。If the amount is less than 1 part by weight, the durability of the cured inorganic material will be poor, and if it exceeds 100 parts by weight, the mechanical strength of the cured inorganic material will be reduced.

【００３７】発泡剤（Ｅ）としては、過酸化水素、過酸
化ナトリウム、過酸化カリウム、過ほう酸ナトリウム等
の過酸化物、或いはＭｇ、Ｃａ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃ
ｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ａｌ、Ｇａ、Ｓｎ、Ｓｉ、フェ
ロシリコン等の金属粉末が挙げられ、コスト、安全性、
入手の容易さ、混合のし易さを考慮すると、これらのう
ち、過酸化水素、アルミニウム粉末が好ましく、発泡反
応の制御のし易さの点を考慮すると、Ｓｉ，フェロシリ
コンが好ましい。Examples of the foaming agent (E) include peroxides such as hydrogen peroxide, sodium peroxide, potassium peroxide and sodium perborate, or Mg, Ca, Cr, Mn, Fe, C
o, Ni, Cu, Zn, Al, Ga, Sn, Si, metal powders such as ferrosilicon, and the like, cost, safety,
Among these, hydrogen peroxide and aluminum powder are preferable in consideration of the availability and ease of mixing, and Si and ferrosilicon are preferable in view of easy control of the foaming reaction.

【００３８】発泡剤（Ｅ）は、ＳｉＯ2−Ａｌ2Ｏ3系の
反応性無機質粉体（Ａ）１００重量部に対して０．０１
〜１０重量部の範囲で添加量が目的とする硬化体の密度
によって決定される。すなわち、添加量が１０重量部を
越えると発泡ガスが過剰となって破砲し、０．０１重量
部を下回ると発泡倍率が小さすぎて硬化体としての意味
を失う。The foaming agent (E) is used in an amount of 0.01 to 100 parts by weight of the SiO 2 —Al 2 O 3 -based reactive inorganic powder (A).
In the range of 10 to 10 parts by weight, the amount to be added is determined by the density of the target cured product. That is, if the addition amount exceeds 10 parts by weight, the foaming gas becomes excessive and the shot is broken. If the addition amount is less than 0.01 part by weight, the expansion ratio is too small to lose the meaning as a cured product.

【００３９】また、過酸化水素を発泡剤（Ｅ）として用
いるときは、水溶液にして用いるのが好ましい。発泡剤
（Ｅ）として使用できる過酸化水素水溶液の濃度は、
０．５〜３５％、好ましくは１〜２５％、さらに好まし
くは５〜１５％とする。濃度が３５％を越えると、発泡
が速くなりすぎ、安定に発泡できない上、危険である。
また、濃度が０．５％を下回ると過酸化水素の量に対す
る水の量が多くなりすぎて粘度が低下し発泡が安定しな
くなるおそれがある。When hydrogen peroxide is used as the blowing agent (E), it is preferable to use it as an aqueous solution. The concentration of the aqueous hydrogen peroxide solution that can be used as the foaming agent (E) is as follows:
0.5 to 35%, preferably 1 to 25%, more preferably 5 to 15%. If the concentration exceeds 35%, the foaming becomes too fast, foaming cannot be performed stably, and it is dangerous.
On the other hand, if the concentration is less than 0.5%, the amount of water becomes too large with respect to the amount of hydrogen peroxide, so that the viscosity may decrease and foaming may not be stabilized.

【００４０】金属粉末を発泡剤（Ｅ）として使用する場
合、その粒径が、平均粒径１〜２００μｍであることが
好ましい。When a metal powder is used as the foaming agent (E), the average particle diameter is preferably 1 to 200 μm.

【００４１】すなわち、平均粒径が２００μｍを越える
と、反応性が低下し、１μｍを下回ると、分散性が低下
するとともに、反応性が高くなって発泡が速くなりすぎ
るおそれがある。That is, when the average particle size exceeds 200 μm, the reactivity is reduced. When the average particle size is less than 1 μm, the dispersibility is reduced, and the reactivity is increased, and the foaming may be too fast.

【００４２】無機質充填材（Ｆ）は、硬化時の収縮低
減、スラリーの流動性向上、セルの緻密化、気泡の安定
化などを図ることができ、例えば、珪砂、珪石粉、スラ
グ、マイカ、タルク、ウォラストナイト、炭酸カルシウ
ム、ゼオライト、活性炭、アルミナゲルなどの多孔質粉
体等が挙げられる。The inorganic filler (F) can reduce shrinkage during curing, improve the fluidity of the slurry, make the cells denser, stabilize the bubbles, and the like. For example, silica sand, silica stone powder, slag, mica, Examples include porous powders such as talc, wollastonite, calcium carbonate, zeolite, activated carbon, and alumina gel.

【００４３】また、無機質充填材（Ｆ）は、平均粒径
０．０１μｍ以上１ｍｍ以下の粒径のものが好ましい。
すなわち、平均粒径１ｍｍを越えると、発泡が安定しな
くなり、０．０１μｍを下回ると吸着水量の増加によっ
て粘度が上がり作業性が低下する。The inorganic filler (F) preferably has an average particle diameter of 0.01 μm or more and 1 mm or less.
That is, if the average particle size exceeds 1 mm, the foaming becomes unstable, and if the average particle size is less than 0.01 μm, the viscosity increases due to an increase in the amount of adsorbed water, and the workability decreases.

【００４４】無機質充填材（Ｆ）の添加量は、ＳｉＯ2
−Ａｌ2Ｏ3系の反応性無機質粉体（Ａ）１００重量部に
対し、７００重量部以下が好ましく、さらに好ましくは
１０〜５００重量部とする。すなわち、添加量が７００
重量部を越えると強度低下を起こすおそれがある。The amount of the inorganic filler (F) added was SiO 2
The amount is preferably 700 parts by weight or less, more preferably 10 to 500 parts by weight, based on 100 parts by weight of the reactive inorganic powder (A) based on -Al 2 O 3 . That is, when the addition amount is 700
If the amount exceeds the weight part, the strength may be reduced.

【００４５】補強繊維（Ｇ）は、強度向上、クラック防
止等を図ることができ、例えば、ビニロン、ポリプロピ
レン、アラミド、アクリル、レーヨン等の有機繊維、カ
ーボン、ガラス、チタン酸カリウム、アルミナ、鋼、ス
ラグウール等の有機繊維が挙げられる。The reinforcing fiber (G) can improve the strength and prevent cracks. For example, organic fibers such as vinylon, polypropylene, aramid, acrylic and rayon, carbon, glass, potassium titanate, alumina, steel, Organic fibers such as slag wool are exemplified.

【００４６】添加される補強繊維（Ｇ）の好ましい繊維
長は、１〜１５ｍｍ、好ましい繊維径は、１〜５００μ
ｍである。The preferable fiber length of the reinforcing fiber (G) to be added is 1 to 15 mm, and the preferable fiber diameter is 1 to 500 μm.
m.

【００４７】繊維長が１５ｍｍを越えると、分散性が低
下し、繊維径が１μｍを下回ると混合時に再凝集し、フ
ァイバーボールが形成されて強度が向上しなくなるおそ
れがあり、繊維長が１ｍｍより下回るか繊維径が５００
μｍを越えると、補強効果が小さい。If the fiber length exceeds 15 mm, the dispersibility decreases, and if the fiber diameter is less than 1 μm, the fibers may re-agglomerate during mixing and fiber balls may be formed and the strength may not be improved. Less than or the fiber diameter is 500
If it exceeds μm, the reinforcing effect is small.

【００４８】補強繊維（Ｇ）の添加量は、ＳｉＯ2−Ａ
ｌ2Ｏ3系の反応性無機質粉体（Ａ）１００重量部に対
し、１０重量部以下が好ましい。すなわち、１０重量部
を越えると、繊維の分散性低下のおそれがある。The amount of the reinforcing fiber (G) added is SiO 2 -A
It is preferably 10 parts by weight or less based on 100 parts by weight of the l 2 O 3 -based reactive inorganic powder (A). That is, if it exceeds 10 parts by weight, the dispersibility of the fiber may be reduced.

【００４９】有機質発泡体や無機質発泡体などの発泡体
（Ｉ）は硬化体の軽量化を図ることができ、有機質発泡
体（Ｉ）としては、塩化ビニル、フェノール、ユリア、
スチレン、ウレタン、エチレンなどの合成樹脂の粒状発
泡体が挙げられ、無機質発泡体（Ｉ）としては、ガラス
バルーン、シラスバルーン、フライアッシュバルーン、
シリカバルーン、パーライト、ヒル石、粒状発泡シリカ
等が挙げられ、これらを単独で又は混合して用いること
ができる。The foam (I) such as an organic foam or an inorganic foam can reduce the weight of the cured product. Examples of the organic foam (I) include vinyl chloride, phenol, urea, and the like.
Granular foams of synthetic resins such as styrene, urethane, ethylene and the like are mentioned. As the inorganic foams (I), glass balloons, shirasu balloons, fly ash balloons,
Examples thereof include silica balloons, perlite, hillite, and particulate expanded silica, and these can be used alone or in combination.

【００５０】上記の発泡体（Ｉ）は、比重が０．０１未
満では、硬化体の機械的強度の低下を招き、また、１を
越えると軽量化の効果が得られなくなるおそれがあるた
め、比重０．０１〜１のものが好ましく、さらに好まし
くは比重が０．０３〜０．７のものとする。If the specific gravity of the foam (I) is less than 0.01, the mechanical strength of the cured product is reduced, and if it exceeds 1, the effect of reducing the weight may not be obtained. The specific gravity is preferably from 0.01 to 1, more preferably from 0.03 to 0.7.

【００５１】上記発泡体（Ｉ）の添加量は、ＳｉＯ2−
Ａｌ2Ｏ3系の反応性無機質粉体（Ａ）１００重量部に対
し、１０〜１００重量部が好ましく、さらに好ましくは
３０〜８０重量部である。すなわち、添加量が１０重量
部を下回ると軽量化の効果が得られず、１００重量部を
越えると機械的強度が低下するおそれがある。The added amount of the foam (I) is SiO 2-
The amount is preferably from 10 to 100 parts by weight, more preferably from 30 to 80 parts by weight, based on 100 parts by weight of the Al 2 O 3 -based reactive inorganic powder (A). That is, if the amount is less than 10 parts by weight, the effect of weight reduction cannot be obtained, and if it exceeds 100 parts by weight, the mechanical strength may be reduced.

【００５２】次に、上記原料を、ミキサー２で混合・混
練し混練物とする（図１ａ）。Next, the above raw materials are mixed and kneaded by a mixer 2 to obtain a kneaded product (FIG. 1a).

【００５３】得られた混練物は、温度が４０℃以下とな
るように、必要に応じて冷却を行い調整する。これは、
この温度以上になると、発泡が早く起こってしまうから
である。The obtained kneaded material is cooled and adjusted as necessary so that the temperature is 40 ° C. or less. this is,
If the temperature is higher than this, foaming occurs quickly.

【００５４】尚、混練物の温度を２０℃以下にすると、
発泡開始時間を遅延させることができるので、好まし
い。このため、非発泡の材料として作り置きして注型を
終了するまでの間多量に貯蔵しておくことが可能となる
ので、有利である。When the temperature of the kneaded material is set to 20 ° C. or less,
This is preferable because the foaming start time can be delayed. This is advantageous because it is possible to make a large amount of non-foamed material and store it until casting is completed.

【００５５】この混練物を、成形用型１の下型３内に注
型し（図１ｂ）、成形用型１が密閉構造であるならば下
型３に補強筋を備えた蓋４をして発泡させる（図１
ｃ）。The kneaded material is poured into the lower mold 3 of the molding die 1 (FIG. 1b). If the molding die 1 has a closed structure, the lower die 3 is covered with a lid 4 having reinforcing bars. To foam (Fig. 1
c).

【００５６】注型後に６０℃以上の温度に加熱すると、
混練物は発泡に必要な温度にまで昇温されて短時間で発
泡を終えるので、プロセス上の取扱いが便利となり、且
つ、生産性の向上も得られる。When heated to a temperature of 60 ° C. or more after casting,
Since the kneaded material is heated to a temperature necessary for foaming and foaming is completed in a short time, handling in the process is convenient and productivity can be improved.

【００５７】混練物が十分に発泡したら、補強筋を取り
込んだ混練物を成形用型１ごと加熱炉５で加熱し脱水縮
重合反応を起こさせて硬化させる（図１ｄ）。When the kneaded product is sufficiently foamed, the kneaded product incorporating the reinforcing bars is heated together with the molding die 1 in the heating furnace 5 to cause a dehydration-condensation polymerization reaction and to cure (FIG. 1d).

【００５８】硬化温度は、常温でもよいが、５０〜２０
０℃に加熱することにより、硬化反応を促進でき、且
つ、得られる硬化体の機械的強度を向上することができ
る。The curing temperature may be room temperature, but may be from 50 to 20.
By heating to 0 ° C., the curing reaction can be promoted, and the mechanical strength of the obtained cured product can be improved.

【００５９】その後、本発明では、補強筋が埋設されて
形成された硬化体は、その裏面側となる枠体である蓋４
のみが外され、再使用される（図１ｅ）。そして、硬化
体の表面側（即ち、意匠面側）を下型３の内底部で拘束
した状態のまま硬化体を乾燥炉６へ入れて乾燥し、硬化
体の裏面側から余剰水分を全体の２０％程度先に除去さ
せるようにする（図１ｆ）。Thereafter, in the present invention, the cured body formed by embedding the reinforcing bars is formed by a lid 4 which is a frame on the back side.
Only are removed and reused (FIG. 1e). Then, while the front side (that is, the design surface side) of the cured body is restrained by the inner bottom of the lower mold 3, the cured body is put into the drying furnace 6 and dried, and excess moisture is removed from the back side of the cured body as a whole. About 20% is removed first (FIG. 1f).

【００６０】このときの乾燥温度は、余剰水分が除去可
能な温度であればよいが、４０〜２００℃とするのが好
ましい。乾燥温度が４０℃未満だと乾燥に非常に長い時
間を要し、２００℃を越えると、クラックや反りが発生
する。The drying temperature at this time may be any temperature at which excess moisture can be removed, but is preferably 40 to 200 ° C. If the drying temperature is lower than 40 ° C., a very long time is required for drying. If the drying temperature is higher than 200 ° C., cracks and warpage occur.

【００６１】その後、硬化体を下型３から脱型し（図１
ｇ）、硬化体全体を再び乾燥炉７へ入れて完全に乾燥
し、無機質硬化体を製造する（図１ｈ）。Thereafter, the cured product is released from the lower mold 3 (FIG. 1).
g) The entire cured product is again put into the drying furnace 7 and completely dried to produce an inorganic cured product (FIG. 1h).

【００６２】その後、無機質硬化体は、必要に応じて二
次加工され、出荷される（図１ｉ）。Thereafter, the inorganic cured product is subjected to secondary processing as required and shipped (FIG. 1i).

【００６３】尚、途中、脱型された下型３と蓋４は、そ
れぞれ上流側へ戻されて再利用される。The lower mold 3 and the lid 4 that have been removed from the mold are returned to the upstream side for reuse.

【００６４】このように、本発明では、ＳｉＯ2−Ａｌ2
Ｏ3系反応性無機質粉体（Ａ）、アルカリ金属珪酸塩
（Ｂ）、水（Ｃ）からなる硬化性無機質組成物を混合・
混練し、この混練物を成形用型内に注型し、混練物を成
形用型ごと加熱し脱水縮重合反応を起こさせて硬化させ
た後、発生する余剰水分を硬化体の裏面側から先に除去
し、特に、混練物に含有される水のうち２０％以上を硬
化体の裏面側から先に除去し、無機質硬化体を製造する
ようにしたので、未反応の珪酸イオンなどの可溶成分が
硬化体の裏面側へ移動された状態となり、その後に無機
質硬化体が吸水した場合でも、表面側に化学的変化を伴
う外観変化を生じることが防止される。As described above, in the present invention, SiO 2 —Al 2
A curable inorganic composition comprising an O 3 -based reactive inorganic powder (A), an alkali metal silicate (B), and water (C) is mixed.
After kneading, the kneaded product is poured into a molding die, and the kneaded product is heated together with the molding die to cause a dehydration-condensation polymerization reaction and is cured. In particular, 20% or more of the water contained in the kneaded material is first removed from the back side of the cured product to produce an inorganic cured product. Even when the components are moved to the back side of the cured body and the inorganic cured body subsequently absorbs water, it is possible to prevent the appearance change accompanying the chemical change on the surface side.

【００６５】これにより、耐水性・耐候性に優れた高耐
久性の無機質硬化体を得ることができるようになる。As a result, it is possible to obtain a highly durable inorganic cured product having excellent water resistance and weather resistance.

【００６６】図２は、本発明の第二の実施の形態であ
り、加熱炉５で加熱して硬化体を形成（図２ｄ）した
後、硬化体を下型３と蓋４から完全に脱型し（図２）、
先ず、硬化体の表面側を防水シート８などで覆った状態
にして硬化体を乾燥炉６へ入れて乾燥することにより、
硬化体の裏面側から余剰水分を全体の２０％程度先に除
去し（図２ｋ）、その後、硬化体の表面から防水シート
８を外し、硬化体全体を再び乾燥炉７へ入れて完全に乾
燥し、無機質硬化体を製造する（図２ｈ）ようにしたも
のである。FIG. 2 shows a second embodiment of the present invention, in which a cured body is formed by heating in a heating furnace 5 (FIG. 2 d), and the cured body is completely removed from the lower mold 3 and the lid 4. Mold (Fig. 2)
First, the cured body is placed in a drying furnace 6 and dried while the front side of the cured body is covered with a waterproof sheet 8 or the like.
Excess moisture is removed from the back side of the cured body by about 20% of the whole (FIG. 2k). Thereafter, the waterproof sheet 8 is removed from the surface of the cured body, and the whole cured body is again put into the drying furnace 7 to be completely dried. Then, an inorganic cured product is produced (FIG. 2h).

【００６７】このようにしても、上記実施の形態と同
様、耐水性・耐候性に優れた高耐久性の無機質硬化体を
得ることができる。In this manner, similarly to the above-described embodiment, a highly durable inorganic cured body having excellent water resistance and weather resistance can be obtained.

【００６８】上記以外については、前記実施の形態と同
様の構成を備えており、同様の作用・効果を得ることが
できる。Except for the above, the configuration is the same as that of the above embodiment, and the same operation and effect can be obtained.

【００６９】[0069]

【実施例】本発明の効果を確認するため、以下の実験を
行った。EXAMPLES The following experiments were conducted to confirm the effects of the present invention.

【００７０】実験には、以下の原料を使用した。The following materials were used in the experiment.

【００７１】ＳｉＯ2−Ａｌ2Ｏ3系反応性無機質粉体
（Ａ） メタカオリン１．７Ｋｇを三菱重工業社製の商品名「ウ
ルトラファインミルＡＴ−２０」（ジルコニアボール直
径１０ｍｍ使用、ボール充填率８５％、粉砕助剤として
トリエタノールアミン２５％とエタノール７５％の混合
物を１０ｇ添加）に供給し、９．９Ｋｗｈ／kg（３時間
＊３．３Ｋｗｈ／kg）の機械的エネルギーを作用させて
得た。SiO 2 —Al 2 O 3 -based reactive inorganic powder (A) 1.7 kg of metakaolin was manufactured by Mitsubishi Heavy Industries, Ltd. under the trade name “Ultra Fine Mill AT-20” (zirconia ball diameter 10 mm, ball filling rate 85 %, A mixture of 25% triethanolamine and 75% ethanol as a grinding aid was added to 10 g), and mechanical energy of 9.9 Kwh / kg (3 hours * 3.3 Kwh / kg) was applied. .

【００７２】アルカリ金属珪酸塩（Ｂ） 珪酸カリ水溶液（日本化学工業（株）製 モル比ＳｉＯ
2：Ｋ2Ｏ＝１．４：１．５０％水溶液） 無機質充填材（Ｆ） ８号珪砂（セキモト建材社製） 珪石粉（住友大阪セメント（株）社製 商品名；ファイ
ンシリカ ブレーン値１０００ｃｍ2／ｇ） 上記原料の配合は、表１の通りである。Alkali metal silicate (B) Potassium silicate aqueous solution (manufactured by Nippon Chemical Industry Co., Ltd., molar ratio SiO
2 : K 2 O = 1.4: 1.50% aqueous solution) Inorganic filler (F) No. 8 silica sand (manufactured by Sekimoto Building Materials Co., Ltd.) Silica powder (manufactured by Sumitomo Osaka Cement Co., Ltd., trade name: fine silica Brain value: 1000 cm 2) / G) The composition of the above raw materials is as shown in Table 1.

【００７３】[0073]

【表１】 ・実施例１〜４ 表１の組成物をオムニミキサーに供給して５分間混合し
た。得られた混合物を１５０＊５０＊１０ｍｍの型内に
注入した後、型枠ごと８５℃の熱風乾燥機中で１０時間
加熱させて無機質硬化体を得た。得られた無機質硬化体
を裏面型のみを外し、所定温度で乾燥した。[Table 1] -Examples 1-4 The composition of Table 1 was supplied to the omni mixer and mixed for 5 minutes. The obtained mixture was poured into a mold of 150 * 50 * 10 mm, and then heated together with the mold in a hot air dryer at 85 ° C. for 10 hours to obtain a cured inorganic material. Only the back mold was removed from the obtained inorganic cured product and dried at a predetermined temperature.

【００７４】・比較例１ 表の組成物をオムニミキサーに供給して５分間混合し
た。得られた混合物を１５０＊５０＊１０ｍｍの型内に
注入した後、型枠ごと８５℃の熱風乾燥機中で１０時間
加熱させて無機質硬化体を得た。得られた無機質硬化体
を型枠から全て取外し、５０℃で１０時間乾燥した。Comparative Example 1 The compositions shown in the table were supplied to an omni mixer and mixed for 5 minutes. The obtained mixture was poured into a mold of 150 * 50 * 10 mm, and then heated together with the mold in a hot air dryer at 85 ° C. for 10 hours to obtain a cured inorganic material. The obtained inorganic cured product was all removed from the mold and dried at 50 ° C. for 10 hours.

【００７５】上記のようにして得られた各無機質硬化体
を下記の条件で評価し、結果を表２にまとめた。Each of the inorganic cured products obtained as described above was evaluated under the following conditions, and the results are summarized in Table 2.

【００７６】（１）水の蒸発量測定 （硬化体表面の型枠を外すまでに蒸発した水の重量）／
（最初の混合物中の水の重量）＊１００ （２）熱水試験 得られた無機質硬化体を９８℃の熱水中に２時間浸漬し
た後２４時間乾燥し、試験前後の色差を分光測色計（ミ
ノルタ製 ＣＭ−２００２）で測定した。(1) Measurement of water evaporation (weight of water evaporated until mold on surface of cured product was removed) /
(Weight of water in the first mixture) * 100 (2) Hot water test The obtained cured inorganic material was immersed in hot water of 98 ° C. for 2 hours and then dried for 24 hours, and the color difference before and after the test was measured by spectral colorimetry. It was measured by a total meter (CM-2002 manufactured by Minolta).

【００７７】（３）促進耐候性試験 得られた無機質硬化体をＪＩＳ の５４００に準じて、
５００時間促進耐候性試験に供した後、試験前後の色差
を分光測色計（ミノルタ製 ＣＭ−２００２）で測定し
た。(3) Accelerated weather resistance test The obtained inorganic cured product was subjected to the following method according to JIS 5400.
After being subjected to the accelerated weathering test for 500 hours, the color difference before and after the test was measured with a spectrophotometer (CM-2002 manufactured by Minolta).

【００７８】[0078]

【表２】 上記実験の結果から、耐水性・耐候性に優れた高耐久性
の無機質硬化体が得られることが確認された。[Table 2] From the results of the above experiments, it was confirmed that a highly durable inorganic cured product excellent in water resistance and weather resistance was obtained.

【００７９】尚、本発明は、上述の実施の形態にのみ限
定されるものではなく、本発明の要旨を逸脱しない範囲
内において種々変更を加え得ることは勿論である。Note that the present invention is not limited to the above-described embodiment, and it goes without saying that various modifications can be made without departing from the spirit of the present invention.

【００８０】[0080]

【発明の効果】以上説明したように、本発明の無機質硬
化体の製造方法によれば、意匠面側となる表面側の外観
を良好に維持して、耐水性・耐候性に優れた高耐久性の
無機質硬化体を得ることができるという優れた効果を奏
し得る。As described above, according to the method for producing a cured inorganic material of the present invention, the appearance on the surface side, which is the design surface side, is maintained good, and high durability with excellent water resistance and weather resistance is obtained. An excellent effect of being able to obtain a hardened inorganic cured product can be obtained.

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

【図１】（ａ）〜（ｉ）は本発明の第一の実施の形態に
かかる概略製造工程図である。FIGS. 1A to 1I are schematic manufacturing process diagrams according to a first embodiment of the present invention.

【図２】（ａ）〜（ｉ）は本発明の第二の実施の形態に
かかる概略製造工程図である。FIGS. 2A to 2I are schematic manufacturing process diagrams according to a second embodiment of the present invention.

【符号の説明】[Explanation of symbols]

１ 成形用型 Ａ ＳｉＯ2−Ａｌ2Ｏ3系反応性無機質粉体 Ｂ アルカリ金属珪酸塩 Ｃ 水1 mold A SiO 2 -Al 2 O 3 system reactive inorganic powder B alkali metal silicate C water

Claims (3)

【特許請求の範囲】[Claims] 【請求項１】 ＳｉＯ2−Ａｌ2Ｏ3系反応性無機質粉
体、アルカリ金属珪酸塩、水からなる硬化性無機質組成
物を混合し、板状に成形し、脱水縮重合反応を起こさせ
て硬化させた後、発生する余剰水分を硬化体の裏面側か
ら先に除去し、無機質硬化体を製造することを特徴とす
る無機質硬化体の製造方法。1. A curable inorganic composition comprising an SiO 2 —Al 2 O 3 -based reactive inorganic powder, an alkali metal silicate and water is mixed, formed into a plate, and subjected to a dehydration-condensation polymerization reaction. A method for producing an inorganic cured body, comprising: removing an excess water generated after curing, from the back side of the cured body, to produce an inorganic cured body. 【請求項２】 混練物に含有される水のうち２０％以上
を硬化体の裏面側から先に除去することを特徴とする請
求項１記載の無機質硬化体の製造方法。2. The method for producing an inorganic cured product according to claim 1, wherein at least 20% of water contained in the kneaded material is removed from the back side of the cured product. 【請求項３】 表面側型枠と裏面側型枠とからなる成形
用型内に注型し、脱型に際し、前記硬化体の前記裏面側
型枠を除去し、所定量の水が蒸発した後、前記表面側型
枠を除去することを特徴とする請求項１記載の無機質硬
化体の製造方法。3. A mold is poured into a molding die composed of a front-side mold and a back-side mold, and upon demolding, the back-side mold of the cured product is removed, and a predetermined amount of water evaporates. 2. The method for producing an inorganic cured product according to claim 1, further comprising removing the front side mold.
JP32672597A 1997-11-27 1997-11-27 Production of cured inorganic material Pending JPH11156838A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP32672597A JPH11156838A (en) 1997-11-27 1997-11-27 Production of cured inorganic material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP32672597A JPH11156838A (en) 1997-11-27 1997-11-27 Production of cured inorganic material

Publications (1)

Publication Number Publication Date
JPH11156838A true JPH11156838A (en) 1999-06-15

Family

ID=18190987

Family Applications (1)

Application Number Title Priority Date Filing Date
JP32672597A Pending JPH11156838A (en) 1997-11-27 1997-11-27 Production of cured inorganic material

Country Status (1)

Country Link
JP (1) JPH11156838A (en)

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