JPH10167799A - Calcium silicate molding product and vacuum heat-insulating material using the same - Google Patents
Calcium silicate molding product and vacuum heat-insulating material using the sameInfo
- Publication number
- JPH10167799A JPH10167799A JP32520896A JP32520896A JPH10167799A JP H10167799 A JPH10167799 A JP H10167799A JP 32520896 A JP32520896 A JP 32520896A JP 32520896 A JP32520896 A JP 32520896A JP H10167799 A JPH10167799 A JP H10167799A
- Authority
- JP
- Japan
- Prior art keywords
- calcium silicate
- alkali metal
- slurry
- insulating material
- vacuum heat
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/18—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mixtures of the silica-lime type
- C04B28/186—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mixtures of the silica-lime type containing formed Ca-silicates before the final hardening step
- C04B28/188—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mixtures of the silica-lime type containing formed Ca-silicates before the final hardening step the Ca-silicates being present in the starting mixture
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5007—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with salts or salty compositions, e.g. for salt glazing
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0004—Compounds chosen for the nature of their cations
- C04B2103/0006—Alkali metal or inorganic ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はケイ酸カルシウム成
形体およびそれを芯材とした真空断熱材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a calcium silicate molded product and a vacuum heat insulating material using the same as a core material.
【０００２】[0002]
【従来の技術】ケイ酸カルシウムは、これまで、保温
材、断熱材として広く使用されている。近年、断熱性能
を向上させたケイ酸カルシウム成形体を芯材として用い
た真空断熱材が提案されている。断熱性能を向上させる
方法としては、繊維状物質、輻射遮蔽材を配合する方法
が提案されている。例えば、に輻射遮蔽材の混合層を設
ける方法（特公平４−４９９８号公報）、輻射遮蔽材を
配合する方法（特開昭５８−１４５６５２号公報）など
が挙げられる。2. Description of the Related Art Calcium silicate has been widely used as a heat insulator and a heat insulator. In recent years, a vacuum heat insulating material using a calcium silicate molded body having improved heat insulating performance as a core material has been proposed. As a method of improving the heat insulation performance, a method of blending a fibrous substance and a radiation shielding material has been proposed. For example, a method of providing a mixed layer of a radiation shielding material (Japanese Patent Publication No. 4-4998), a method of blending a radiation shielding material (Japanese Patent Application Laid-Open No. 58-145652) and the like can be mentioned.
【０００３】また、ケイ酸カルシウム成形体を芯材とす
る真空断熱材としては、ケイ酸カルシウム成形体中のパ
ルプを燃焼消失させたものを芯材とするもの（特公平４
−６０９５０号公報）輻射遮蔽材を含有するケイ酸カル
シウムを芯材とするもの（ＷＯ ９５／１４８８１号公
報）などが知られている。[0003] Further, as a vacuum heat insulating material having a calcium silicate molded body as a core material, a material obtained by burning and eliminating pulp in a calcium silicate molded body as a core material (Japanese Patent Application Publication No.
Japanese Unexamined Patent Publication No. 60950/1985) and those using calcium silicate containing a radiation shielding material as a core material (WO 95/14881) are known.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、これら
のケイ酸カルシウム成形体は、粉っぽいという問題があ
る。粉っぽいケイ酸カルシウム成形体は、ケイ酸カルシ
ウム粒子が空気中へ飛散し、これにより作業環境の悪化
を招き、取扱性が悪さを指摘されている。また、ケイ酸
カルシウム成形体を真空断熱材の芯材として用いたとき
には、真空包装時に余分な粉体が包材に付着し、シール
不良で真空度の経年劣化上昇をもたらす危険もある。However, these calcium silicate compacts have a problem that they are powdery. It has been pointed out that the powdery calcium silicate molded body has calcium silicate particles scattered into the air, thereby deteriorating the working environment and poor handling properties. Further, when the calcium silicate molded body is used as a core material of a vacuum heat insulating material, excess powder adheres to the packaging material at the time of vacuum packaging, and there is a danger of causing deterioration of the degree of vacuum over time due to poor sealing.
【０００５】ケイ酸カルシウム成形体の粉っぽさを低減
するためには、ケイ酸カルシウム成形体の比重を上げる
ことが有効であるが、これは熱伝導率の上昇を招き、真
空断熱芯材としての性能の低下を招く。また、有機物を
ケイ酸カルシウムのバインダーとして用いることも考え
られるが、真空包装後に有機バインダーが気化すること
により真空度が低下する恐れもある。In order to reduce the powderiness of the calcium silicate molded product, it is effective to increase the specific gravity of the calcium silicate molded product. Causes a decrease in performance. It is also conceivable to use an organic substance as a binder of calcium silicate, but there is a possibility that the degree of vacuum may be reduced due to vaporization of the organic binder after vacuum packaging.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記問題
に鑑み鋭意検討した結果、特定の無機化合物を添加する
ことにより、ケイ酸カルシウム成形体の表面の粉化が効
果的に防止できることを見出し、本発明に到達した。即
ち、本発明の要旨は、アルカリ金属の硫酸塩、塩化物お
よびゼオライトから選ばれる少なくとも１種を含むこと
を特徴とする、比重が０．１以下の珪酸カルシウム成形
体に存する。Means for Solving the Problems The present inventors have made intensive studies in view of the above problems, and as a result, it has been found that powdering of the surface of a calcium silicate molded article can be effectively prevented by adding a specific inorganic compound. And arrived at the present invention. That is, the gist of the present invention resides in a calcium silicate molded article having a specific gravity of 0.1 or less, characterized by containing at least one selected from alkali metal sulfates, chlorides and zeolites.
【０００７】[0007]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明のケイ酸カルシウム成形体は、通常、ケイ酸カル
シウムのスラリーを脱水成形することにより得られる。
ケイ酸カルシウムとしては、通常、ゾノトライト、トバ
モライト等の結晶質のもの、ＣＳＨ 、ＣＳＨ 等の低
結晶性のもの、非晶質のものいずれでもよく、好ましく
は、結晶質のものが用いられる。このようなケイ酸カル
シウムは、通常、石灰質原料とケイ酸質原料を、水熱合
成反応させることにより得られる。石灰質原料として
は、生石灰、消石灰などが挙げられる。石灰質原料は、
通常、嵩高の石灰粒子を含有する石灰乳に調整して使用
される。ケイ酸質原料としては、非晶質、結晶質のいず
れでも良く、具体的には、珪藻土、珪石、石英などの天
然品、シリコンダストなどの工業副産物等が挙げられ
る。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The calcium silicate molded article of the present invention is usually obtained by subjecting a slurry of calcium silicate to dehydration molding.
As the calcium silicate, any of crystalline ones such as zonotolite and tobermorite, low-crystalline ones such as CSH 2 and CSH 2 and amorphous ones may be used, and crystalline ones are preferably used. Such calcium silicate is usually obtained by subjecting a calcareous raw material and a siliceous raw material to a hydrothermal synthesis reaction. Examples of calcareous raw materials include quicklime and slaked lime. Calcareous raw materials are
Usually, it is used by adjusting to lime milk containing bulky lime particles. The siliceous raw material may be either amorphous or crystalline. Specific examples include natural products such as diatomaceous earth, silica stone and quartz, and industrial by-products such as silicon dust.
【０００８】ケイ酸カルシウムの製法としては、ゾノト
ライトを例に挙げると、ＣａＯ：ＳｉＯ2 のモル比が
４：５〜１３：１０である、石灰質原料とケイ酸質原料
を含む水スラリーを加圧下、１６０℃以上で２〜４８時
間、水熱合成する方法が挙げられる。水熱合成により得
られたケイ酸カルシウムスラリーは、そのまま脱水成形
してケイ酸カルシウム成形体にしても、乾燥させたケイ
酸カルシウムを水に添加してスラリーとしたものを脱水
成形してケイ酸カルシウム成形体にしもよい。ケイ酸カ
ルシウム成形体を作成するためのスラリー中のケイ酸カ
ルシウムの固形分濃度は特に制限はないが、通常５％以
下である。比重が０．０５以下の低比重のケイ酸カルシ
ウム成形体を製造する場合は、２〜４％が好ましい。As a method for producing calcium silicate, for example, using zonotolite, a water slurry containing a calcareous raw material and a siliceous raw material having a molar ratio of CaO: SiO 2 of 4: 5 to 13:10 is applied under pressure. And hydrothermal synthesis at 160 ° C. or higher for 2 to 48 hours. The calcium silicate slurry obtained by hydrothermal synthesis is directly dehydrated and formed into a calcium silicate molded body, and dried calcium silicate is added to water to form a slurry, and the slurry is dehydrated and formed. It may be a calcium compact. The solid concentration of calcium silicate in the slurry for preparing the calcium silicate molded body is not particularly limited, but is usually 5% or less. When producing a low specific gravity calcium silicate molded article having a specific gravity of 0.05 or less, 2 to 4% is preferable.
【０００９】このようにして得られたケイ酸カルシウム
成形体は、比重が０．１以下、好ましくは０．０７〜
０．０３である。比重が０．１を超えると熱伝導率が高
くなるので好ましくない。本発明は、比重０．１以下の
ケイ酸カルシウム成形体が、アルカリ金属の硫酸塩、塩
化物またはゼオライトを含有することを特徴とする。ア
ルカリ金属としては、通常ナトリウム、カリウムが用い
られる。具体的には、アルカリ金属の硫酸塩としては、
硫酸ナトリウム、硫酸カリウム、アルカリ金属の塩化物
としては、塩化ナトリウム、塩化カリウム等が挙げられ
る。これらは結晶水を含む化合物であっても、無水物で
あってもよい。ゼオライトとしては、天然、合成のいず
れのゼオライトを用いてることができる。合成ゼオライ
トには大まかに吸着・触媒用、洗剤用に大別されるがい
ずれのものも使用できる。（以下、アルカリ金属の硫酸
塩、塩化物及びゼオライトをまとめて「粉化防止剤」と
いうこともある。）これらの粉化防止剤は、１種類を用
いても、２種以上を併用してもよい。The calcium silicate compact obtained in this way has a specific gravity of 0.1 or less, preferably 0.07 to less.
0.03. When the specific gravity exceeds 0.1, the thermal conductivity increases, which is not preferable. The present invention is characterized in that the calcium silicate molded body having a specific gravity of 0.1 or less contains an alkali metal sulfate, chloride or zeolite. Sodium and potassium are usually used as the alkali metal. Specifically, as sulfates of alkali metals,
Examples of sodium sulfate, potassium sulfate, and alkali metal chlorides include sodium chloride and potassium chloride. These may be compounds containing water of crystallization or anhydrides. As the zeolite, any of natural and synthetic zeolites can be used. Synthetic zeolites are roughly classified into those for adsorption / catalysis and those for detergents, and any of them can be used. (Hereinafter, alkali metal sulfates, chlorides and zeolites may be collectively referred to as "anti-powders.") These anti-powders may be used alone or in combination of two or more. Is also good.
【００１０】アルカリ金属の硫酸塩、塩化物またはゼオ
ライトを含有することによりケイ酸カルシウム成形体の
粉化が効果的に防止できる理由は明らかではないが、本
発明のケイ酸カルシウム成形体は、ケイ酸カルシウムの
結晶が形成する２次粒子同士が物理的に付着して強度を
保つ構造をしているのと共に、粉化防止剤に由来する無
機物質がケイ酸カルシウム粒子をつなぐ橋掛け構造をし
ているため、すなわち、無機物質がケイ酸カルシウム粒
子をつなぐバインダーの役割をしているためと推測され
る。この橋掛け構造は、粉化防止剤をスラリーに添加し
た場合は、成形体全体に存在し、また、成形体に塗布、
散布または含浸させた場合は、表層近くのみに存在する
と考えられる。Although it is not clear why the calcium silicate molded product can be effectively prevented from being powdered by containing an alkali metal sulfate, chloride or zeolite, the calcium silicate molded product of the present invention does not The secondary particles formed by the calcium silicate crystals have a structure that physically adheres to each other to maintain the strength, and the inorganic substance derived from the powdering inhibitor has a cross-linking structure that connects the calcium silicate particles. That is, it is presumed that the inorganic substance plays a role of a binder connecting the calcium silicate particles. This bridging structure exists in the entire molded body when the powdering inhibitor is added to the slurry, and is applied to the molded body.
When sprayed or impregnated, it is considered to be present only near the surface layer.
【００１１】粉化防止剤をケイ酸カルシウム成形体に含
有させる方法は特に限定されないが、（１）粉化防止剤
がケイ酸カルシウムの生成を阻害しない場合は、ケイ酸
カルシウムを製造する際にケイ酸質原料、石灰質原料と
ともに粉化防止剤を配合して水スラリーとし、これを水
熱合成し、粉化防止剤を含有するケイ酸カルシウムスラ
リーを得て、これを成形し、ケイ酸カルシウム成形体と
する方法、（２）ケイ酸カルシウム成形体に粉化防止剤
の水性液を塗布、散布または含浸させる方法、ここで、
水性液は、アルコールなどの有機溶媒を含んでいてもよ
く、水性液は、水溶液、懸濁液のいずれであってもよ
い。また、水性液の濃度は、通常１〜３０重量％であ
る。（３）ケイ酸カルシウムスラリーに粉化防止剤を添
加し、これを成形する方法、などが挙げられる。少量の
粉化防止剤の使用で、効果的に粉化が防止できるので、
（２）の方法が好ましく用いられる。The method for incorporating the powdering inhibitor into the calcium silicate molded body is not particularly limited, but (1) when the powdering inhibitor does not inhibit the production of calcium silicate, A siliceous raw material and a calcareous raw material are blended with a powdering inhibitor to form a water slurry, which is hydrothermally synthesized to obtain a calcium silicate slurry containing the powdering inhibitor, which is formed and formed into a calcium silicate slurry. A method of forming a molded body, (2) a method of applying, spraying or impregnating an aqueous liquid of a powdering inhibitor on a calcium silicate molded body,
The aqueous liquid may contain an organic solvent such as an alcohol, and the aqueous liquid may be any of an aqueous solution and a suspension. The concentration of the aqueous liquid is usually 1 to 30% by weight. (3) A method of adding a powdering inhibitor to a calcium silicate slurry and molding the same. By using a small amount of powdering inhibitor, powdering can be effectively prevented,
The method (2) is preferably used.
【００１２】粉化防止剤の含有量は、（２）の方法で製
造した場合は、ケイ酸カルシウム成形体の表面に、通常
２〜２０ｍｇ／ｃｍ2、（１）または（３）の方法で製
造した場合は、ケイ酸カルシウム１００重量部に対し、
通常５〜２０重量部である。粉化防止剤の含有量が少な
すぎると粉化防止の効果が十分に得られず、多すぎると
ケイ酸カルシウム成形体の比重および熱伝導率が大きく
なり、また、粉化防止効果も頭打ちである。ケイ酸カル
シウム成形体に粉化防止剤の溶液を添付、散布または含
浸させた場合は、その後、通常１００〜２００℃の温度
にて、通常５〜３０時間、乾燥される。上記方法で得ら
れた成形体の見かけ密度は０．０２〜０．１ｇ／ｃ
ｍ3、圧縮強度は通常１Ｋｇ／ｃｍ2以上、好ましくは
１．５〜６Ｋｇ／ｃｍ2である。When the powdering inhibitor is prepared by the method (2), the content of the powdering inhibitor is usually 2 to 20 mg / cm 2 on the surface of the calcium silicate molded product by the method (1) or (3). When manufactured, for 100 parts by weight of calcium silicate,
Usually, it is 5 to 20 parts by weight. If the content of the powdering inhibitor is too small, the effect of preventing powdering cannot be sufficiently obtained, and if it is too large, the specific gravity and the thermal conductivity of the calcium silicate molded product increase, and the effect of preventing powdering also reaches a peak. is there. When the calcium silicate molded body is attached, sprayed or impregnated with the solution of the powdering inhibitor, it is then dried at a temperature of usually 100 to 200 ° C., usually for 5 to 30 hours. The apparent density of the molded article obtained by the above method is 0.02 to 0.1 g / c.
m 3 and the compressive strength are usually 1 kg / cm 2 or more, preferably 1.5 to 6 kg / cm 2 .
【００１３】本発明のケイ酸カルシウム成形体は、繊維
状物質、輻射遮蔽材を含有していてもよい。繊維状物質
としては、従来公知の繊維状物質を用いることができ、
具体的には、ガラス繊維、炭素繊維、有機繊維、パルプ
等が挙げられる。これらは単独、もしくは２種以上混合
しても良い。繊維状物質を含有しているとケイ酸カルシ
ウム成形体の強度が向上するので好ましい。輻射遮蔽材
としては、通常、炭化珪素、酸化チタン等が用いられ
る。輻射熱吸収材を含有していると断熱効果が向上する
ので好ましい。[0013] The calcium silicate molded article of the present invention may contain a fibrous substance and a radiation shielding material. As the fibrous substance, a conventionally known fibrous substance can be used,
Specifically, glass fiber, carbon fiber, organic fiber, pulp and the like can be mentioned. These may be used alone or as a mixture of two or more. It is preferable to contain a fibrous substance because the strength of the calcium silicate molded body is improved. As the radiation shielding material, silicon carbide, titanium oxide, or the like is usually used. It is preferable to include a radiant heat absorber since the heat insulating effect is improved.
【００１４】本発明のケイ酸カルシウム成形体を真空断
熱材の芯材として用いる場合は、ケイ酸カルシウム成形
体を容器内に収容した後、容器内が減圧状態となるよう
にして排気し、次いで成形体を減圧状態で密着包装する
ことにより、真空断熱材を製造することができる。この
場合、ケイ酸カルシウム成形体を密着包装する前に、通
常３００℃以上、好ましくは３００〜５００℃の温度
で、通常１〜５時間加熱処理することが望ましい。この
加熱処理によりケイ酸カルシウム成形体の吸着水が除去
され、加熱処理のない場合と比べて一層優れた断熱性能
をえることができる。When the calcium silicate molded product of the present invention is used as a core material of a vacuum heat insulating material, after the calcium silicate molded product is housed in a container, the container is evacuated to a reduced pressure state, and then evacuated. A vacuum heat insulating material can be manufactured by tightly packing the molded body under reduced pressure. In this case, it is desirable to heat-treat the calcium silicate molded body at a temperature of usually 300 ° C. or higher, preferably 300 to 500 ° C., usually for 1 to 5 hours before tightly packaging. By this heat treatment, the adsorbed water of the calcium silicate molded body is removed, and more excellent heat insulating performance can be obtained as compared with the case without the heat treatment.
【００１５】真空断熱材に用いられる容器としては、公
知のプラスチックフィルムに金属箔を積層したもの、プ
ラスチックフィルムに金属または金属酸化物を蒸着した
複合フィルムが使用できる。このような複合フィルムは
ガスバリアー性でかつ可橈性を有するので好適に用いら
れる。容器の形状は、通常、両端開放の筒状体が用いら
れる。このようにして得られた真空断熱材は、例えば、
電気冷蔵庫、冷凍車、冷蔵貨物、家屋（建築用）などの
断熱材として好適に使用し得る。As the container used for the vacuum heat insulating material, a known plastic film laminated with a metal foil or a composite film formed by depositing a metal or metal oxide on a plastic film can be used. Such a composite film is suitably used because it has gas barrier properties and flexibility. As the shape of the container, a cylindrical body open at both ends is usually used. The vacuum insulation material obtained in this way is, for example,
It can be suitably used as a heat insulating material for electric refrigerators, refrigerator cars, refrigerated cargo, houses (for construction), and the like.
【００１６】[0016]
【実施例】以下、本発明を実施例により更に詳細に説明
するが、本発明はその要旨を越えない限り下記の実施例
に限定されるものではない。ケイ酸カルシウムの原料と
して、生石灰は、矢橋工業製 軽焼き生石灰（CaO９
６．２０％、Al2O3 ０．０６％、MgO １．２９％ 、Fe2
O3 ０．０３１％、Ig.loss １．１２％）を、珪石は、
東海工業製 伊豆特粉（SiO2 96.64% Al2O3 1.23% Fe2O
3 0.107% Ig.loss 0.89%）を使用した。また、ケイ酸カ
ルシウム成形体の粉っぽさを判断するためのスウィープ
試験は、次のように行った。EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention. As a raw material of calcium silicate, quicklime is lightly burnt quicklime (CaO9
6.20%, Al 2 O 3 0.06 %, 1.29% MgO, Fe 2
O 3 0.031%, Ig.loss 1.12%)
Tokai Kogyo Izu Special Powder (SiO 2 96.64% Al 2 O 3 1.23% Fe 2 O
3 0.107% Ig.loss 0.89%) was used. In addition, a sweep test for determining the powderiness of the calcium silicate molded body was performed as follows.
【００１７】まず、ケイ酸カルシウム成形体の表面と垂
直に刷毛（豚毛２５ｍｍ８号）を接触させる。次いで、
この刷毛を成形体の表面に接触させたまま１５ｃｍ移動
させる。この時刷毛についた粉をメンディングテープ
（住友３Ｍ社製）に付着させ、このテープを黒色の画用
紙にはりつける。粉が多く剥離したものはテープに白く
現れており、粉がほとんど剥離しないものはテープは画
用紙の黒を移して黒いままである。テープに付着したケ
イ酸カルシウムの粉の量を以下の方法で定量した。上記
テープを台紙に貼り付け、シャープ社製カラースキャナ
ーＪＸ−６００を用いて、デジタル画像として入力し
た。このときのγ＝１、解像度は２５０ｌｉｎｅ／ｉｎ
ｃｈとした。画像処理ソフトは、三菱化学社製ＭＫＳＩ
ＰＳ１０００を用い、入力画像の視野から各テープ毎
に、縦×横＝１０１×４４６画素領域を切り取り、各画
素の輝度を最も暗いレベルから最も明るいレベルまで、
明るさに応じて、０〜２５５までの２５６段階にデジタ
ル変換し、各対象領域内の輝度の累積値を累積輝度値と
して算出した。First, a brush (pig wool 25 mm8) is brought into contact with the surface of the calcium silicate molded product vertically. Then
The brush is moved 15 cm while keeping the brush in contact with the surface of the molded body. At this time, the powder attached to the brush is attached to a mending tape (manufactured by Sumitomo 3M), and the tape is attached to black construction paper. Those with much powder peeling appear white on the tape, and those with little powder peeling leave the black of the drawing paper as black. The amount of calcium silicate powder adhering to the tape was determined by the following method. The tape was affixed to a backing paper, and input as a digital image using a color scanner JX-600 manufactured by Sharp Corporation. At this time, γ = 1 and the resolution is 250 line / in.
ch. Image processing software is MKSI manufactured by Mitsubishi Chemical Corporation.
Using PS1000, a vertical x horizontal = 101 x 446 pixel area is cut out from the visual field of the input image for each tape, and the brightness of each pixel is changed from the darkest level to the brightest level.
Digital conversion was performed in 256 steps from 0 to 255 in accordance with the brightness, and the cumulative value of the luminance in each target area was calculated as the cumulative luminance value.
【００１８】＜実施例１＞生石灰４９．６重量部に温水
を加え、９５℃で５分間消和し、消石灰スラリーとし、
このスラリーを超音波分散機で超音波を２０分間照射し
て消石灰乳を得た。一方、珪石５０．４重量部を水中に
分散し珪石スラリーを得た。これらの消石灰乳と珪石ス
ラリーを混合し、総水量が固形分に対し３８重量倍とな
るように水を加えた。このスラリーをオートクレーブ中
で２０４℃、約１７Ｋｇ／ｃｍ2の水蒸気圧下で撹拌し
ながら１６５分間反応を行い、ケイ酸カルシウム（ゾノ
トライト）のスラリーを得た。Example 1 Warm water was added to 49.6 parts by weight of quicklime and slaked at 95 ° C. for 5 minutes to form a slaked lime slurry.
The slurry was irradiated with ultrasonic waves for 20 minutes using an ultrasonic disperser to obtain slaked lime milk. Separately, 50.4 parts by weight of silica was dispersed in water to obtain a silica slurry. These slaked lime milk and silica stone slurry were mixed, and water was added so that the total amount of water was 38 times by weight with respect to the solid content. The slurry was reacted in an autoclave at 204 ° C. under a steam pressure of about 17 kg / cm 2 for 165 minutes to obtain a calcium silicate (zonotolite) slurry.
【００１９】強化繊維として、１８ｍｍに切断したチョ
ップドストランドからなる炭素繊維とパルプを用いた。
これら繊維はスラリーと混合前にあらかじめミキサーで
水中に分散しておいた。前記ケイ酸カルシウムスラリー
にケイ酸カルシウムの固形分９８重量％に対し、炭素繊
維１重量％、パルプ１重量％を添加し混合した後、濾水
面に予め不織布がはってある、２２（ｃｍ）×２２（ｃ
ｍ）の濾水成型機の金型に供給した。これを加圧、脱水
し、１０５℃で２１時間乾燥して、厚み２４ｍｍ、比重
０．０５ｇ／ｃｍ3の成形体を得た。As the reinforcing fibers, carbon fibers made of chopped strands cut into 18 mm and pulp were used.
These fibers were previously dispersed in water with a mixer before mixing with the slurry. After adding and mixing 1% by weight of carbon fiber and 1% by weight of pulp with respect to the solid content of calcium silicate to 98% by weight of the calcium silicate slurry, a nonwoven fabric is previously attached to the drainage surface, 22 (cm). × 22 (c
m) to the mold of the drainage molding machine. This was pressurized, dehydrated and dried at 105 ° C. for 21 hours to obtain a molded product having a thickness of 24 mm and a specific gravity of 0.05 g / cm 3 .
【００２０】この成形体の表面に、１０重量％硫酸ナト
リウム水溶液を５ｍｇ／ｃｍ2の割合で噴霧し、１０５
℃で２１時間乾燥した後、３００℃で５時間加熱し、成
形体を完全に乾燥させ、芯材としてのケイ酸カルシウム
成形体を得た。この芯材の比重を測定し、粉っぽさの評
価としてスウィープ試験を行った。比重を表−２に、ス
ウィープ試験の結果を表−３に示す。A 10% by weight aqueous solution of sodium sulfate was sprayed onto the surface of the molded body at a rate of 5 mg / cm 2 ,
After drying at 21 ° C. for 21 hours, the mixture was heated at 300 ° C. for 5 hours to completely dry the molded body to obtain a calcium silicate molded body as a core material. The specific gravity of the core material was measured, and a sweep test was performed as an evaluation of powderiness. Table 2 shows the specific gravity, and Table 3 shows the results of the sweep test.
【００２１】次に、ポリエチレンテレフタレートフィル
ム（１２μｍ）／アルミニウム箔（９μｍ）／ポリプロ
ピレンフィルム（６０μｍ）の構成をした積層フィルム
よりなる、ポリプロピレンフィルムを内層とする両端開
放の筒状容器のほぼ中央に、上記の成形体を配置し、真
空室容積２０リットル、排気量５００リットル／分の性
能を備えた真空包装機に収容して排気処理を行った。真
空室のゲージ圧が０．０５Ｔｏｒｒ付近に達した時点で
容器両端の開口部をヒートシールして密着包装し、ケイ
酸カルシウム成形体を断熱芯材とする真空断熱材を得
た。得られた真空断熱材の熱伝導率を測定した。結果を
表−２に示す。Next, at the substantially center of a cylindrical container having a polypropylene film as an inner layer and having both ends open, comprising a laminated film having a structure of polyethylene terephthalate film (12 μm) / aluminum foil (9 μm) / polypropylene film (60 μm). The above compact was placed in a vacuum packaging machine equipped with a vacuum chamber having a capacity of 20 liters and a displacement of 500 liters / minute, and was evacuated. When the gauge pressure in the vacuum chamber reached about 0.05 Torr, the openings at both ends of the container were heat-sealed and closely packed to obtain a vacuum heat insulating material using a calcium silicate molded body as a heat insulating core. The thermal conductivity of the obtained vacuum heat insulating material was measured. Table 2 shows the results.
【００２２】＜実施例２＞ケイ酸カルシウムを生成する
のに総水量を固形分に対し３７重量倍にして、原料スラ
リーをオートクレーブ中で２０４℃の温度（約１７Ｋｇ
／ｃｍ2の水蒸気圧下）で４時間反応を行った他は、実
施例１と同様に行って、ケイ酸カルシウム（ゾノトライ
ト）スラリーを得た。得られたケイ酸カルシウムスラリ
ーに、実施例１と同様に、ケイ酸カルシウムの固形分９
８重量％に対し、炭素繊維１重量％、パルプ１重量％を
混合した。このスラリーの固形物１００重量部に対し、
無水硫酸ナトリウムを１０重量部を添加して混合した。
次いで、これを用いて実施例１と同様にして、厚さ２０
ｍｍ、比重０．０５５のケイ酸カルシウム成形体を得
た。Example 2 The total amount of water was 37 times the solid content to produce calcium silicate, and the raw material slurry was placed in an autoclave at a temperature of 204 ° C. (about 17 kg).
/ Cm 2 under a steam pressure of 4 hours), except that the reaction was carried out for 4 hours, to obtain a calcium silicate (zonotlite) slurry. As in Example 1, the solid content of calcium silicate 9 was added to the obtained calcium silicate slurry.
1% by weight of carbon fiber and 1% by weight of pulp were mixed with 8% by weight. For 100 parts by weight of the solid matter of this slurry,
10 parts by weight of anhydrous sodium sulfate was added and mixed.
Then, using this, in the same manner as in Example 1, the thickness 20
mm and a specific gravity of 0.055 were obtained.
【００２３】次いで、これを３００℃で５時間加熱し、
成形体を完全に乾燥させ、芯材としてのケイ酸カルシウ
ム成形体を得た。得られた芯材の比重を測定し、スウィ
ープ試験を行った。比重を表−２にスイープ試験の結果
を表−３に示す。表−３より、粉体の剥離がほとんどな
いことが分かる。この芯材を用いて実施例１と同様にし
て真空断熱材を製造した。この真空断熱材の熱伝導率を
測定した。結果を表−２に示す。Next, this is heated at 300 ° C. for 5 hours,
The molded body was completely dried to obtain a calcium silicate molded body as a core material. The specific gravity of the obtained core material was measured, and a sweep test was performed. Table 2 shows the specific gravity, and Table 3 shows the results of the sweep test. From Table 3, it can be seen that the powder is hardly peeled off. A vacuum heat insulating material was manufactured in the same manner as in Example 1 using this core material. The thermal conductivity of this vacuum heat insulating material was measured. Table 2 shows the results.
【００２４】＜実施例３＞ケイ酸カルシウムを水熱合成
する際の原料スラリーの水固形分比を３８倍量とした他
は実施例２と同様にケイ酸カルシウムを合成した。硫酸
ナトリウムの代わりに、塩化ナトリウムを用いた他は実
施例１と同様に粉化防止剤を噴霧し、ケイ酸カルシウム
成形体および真空断熱材を得た。結果を表−２および表
−３に示す。 ＜実施例４＞実施例３と同じケイ酸カルシウムを用い
た。硫酸ナトリウムの代わりに塩化ナトリウムを用いた
他は、実施例２と同様に粉化防止剤をスラリー中に添加
し、ケイ酸カルシウム成形体を得た。結果を表−２およ
び表−３に示す。Example 3 Calcium silicate was synthesized in the same manner as in Example 2 except that the water solid content ratio of the raw material slurry used for hydrothermal synthesis of calcium silicate was 38 times. A powdering inhibitor was sprayed in the same manner as in Example 1 except that sodium chloride was used instead of sodium sulfate, to obtain a calcium silicate compact and a vacuum heat insulating material. The results are shown in Tables 2 and 3. Example 4 The same calcium silicate as in Example 3 was used. A powdering inhibitor was added to the slurry in the same manner as in Example 2 except that sodium chloride was used instead of sodium sulfate, to obtain a calcium silicate compact. The results are shown in Tables 2 and 3.
【００２５】＜実施例５＞塩化ナトリウムの代わりに硫
酸カリウムを用いた他は実施例３と同様行ってケイ酸カ
ルシウム成形体を得た。結果を表−２および表−３に示
す。 ＜実施例６＞粉化防止剤の散布量を１０ｇ／４００ｃｍ
２に変えた他は実施例５と同様に行ってケイ酸カルシウ
ム成形体を得た。結果を表−２および表−３に示す。 ＜実施例７＞塩化ナトリウムの代わりに硫酸カリウムを
用いた他は実施例４と同様行ってケイ酸カルシウム成形
体を得た。結果を表−２および表−３に示す。Example 5 A calcium silicate compact was obtained in the same manner as in Example 3 except that potassium sulfate was used instead of sodium chloride. The results are shown in Tables 2 and 3. <Example 6> Spraying amount of powdering inhibitor was 10 g / 400 cm.
Except having changed to 2, it carried out similarly to Example 5, and obtained the calcium silicate molded object. The results are shown in Tables 2 and 3. Example 7 A calcium silicate compact was obtained in the same manner as in Example 4 except that potassium sulfate was used instead of sodium chloride. The results are shown in Tables 2 and 3.
【００２６】＜実施例８＞塩化ナトリウムの代わりに硫
酸ナトリウムを用いた他は実施例４と同様行ってケイ酸
カルシウム成形体および真空断熱材を得た。結果を表−
２および表−３に示す。 ＜実施例９＞塩化ナトリウムの代わりにゼオライト（和
光純薬（株）製、商品名ゼオライトＡ−４）を用いた他
は実施例４と同様に行ってケイ酸カルシウム成形体およ
び真空断熱材を得た。結果を表−２および表−３に示
す。Example 8 A calcium silicate compact and a vacuum heat insulating material were obtained in the same manner as in Example 4, except that sodium sulfate was used instead of sodium chloride. Table-Results
2 and Table-3. <Example 9> A calcium silicate molded body and a vacuum heat insulating material were prepared in the same manner as in Example 4, except that zeolite (Zeolite A-4, manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of sodium chloride. Obtained. The results are shown in Tables 2 and 3.
【００２７】＜実施例１０＞水固形分比を４０倍量で合
成したことを除き実施例２と同様にケイ酸カルシウムを
合成した。得られたケイ酸カルシウムスラリーにケイ酸
カルシウムの固形分８３重量％に対し、炭素繊維１重量
％、パルプ１重量％、ＳｉＣ１５重量％を混合した他は
実施例２と同様にケイ酸カルシウム成形体を製造した。
得られた成形体を用いて、実施例１と同様にして、硫酸
ナトリウムを噴霧し、ケイ酸カルシウム成形体を得た。
結果を表−２および表−３に示す。<Example 10> Calcium silicate was synthesized in the same manner as in Example 2 except that the water solid content ratio was 40 times. A calcium silicate formed body was prepared in the same manner as in Example 2 except that the obtained calcium silicate slurry was mixed with 1% by weight of carbon fiber, 1% by weight of pulp, and 15% by weight of SiC with respect to 83% by weight of solid content of calcium silicate. Was manufactured.
Using the obtained compact, sodium sulfate was sprayed in the same manner as in Example 1 to obtain a calcium silicate compact.
The results are shown in Tables 2 and 3.
【００２８】＜比較例１＞実施例１において硫酸ナトリ
ウム水溶液を噴霧しなかった以外は、実施例１と同様に
して芯材の比重、スウィープ試験および真空断熱材の熱
伝導率の測定を行った。その結果を表−２および表−３
に示す。 ＜比較例２＞硫酸ナトリウムを添加したほかは実施例２
と同様に行った。ケイ酸カルシウム成形体の比重および
真空断熱材の熱伝導率を表−２に、スィープ試験の結果
を表−３に示す。 ＜比較例３＞塩化ナトリウムを噴霧なかった他は実施例
３と同様に行った。結果を表−２および表−３に示す。Comparative Example 1 The specific gravity of the core material, the sweep test, and the measurement of the thermal conductivity of the vacuum heat insulating material were performed in the same manner as in Example 1 except that the aqueous sodium sulfate solution was not sprayed. . Table 2 and Table 3 show the results.
Shown in Comparative Example 2 Example 2 except that sodium sulfate was added.
The same was done. Table 2 shows the specific gravity of the calcium silicate compact and the thermal conductivity of the vacuum heat insulating material, and Table 3 shows the results of the sweep test. <Comparative Example 3> The same operation as in Example 3 was carried out except that sodium chloride was not sprayed. The results are shown in Tables 2 and 3.
【００２９】＜比較例４＞硫酸アトリウムを噴霧しなか
った他は実施例１０と同様に行った。結果を表−２およ
び表−３に示す。 ＜比較例５、６および７＞粉化防止剤として、塩化ナト
リウムの代わりに、硫酸マグネシウム（比較例５）、硫
酸アルミニウム（比較例６）、硫酸鉄（ＩＩ）（比較例
７）を用いた他は実施例３と同様に行った。結果を表−
２および表−３に示す。 ＜比較例８、９および１０＞粉化防止剤として、塩化ナ
トリウムの代わりに、硫酸アルミニウム（比較例８）、
硫酸バリウム（比較例９）、硫酸カルシウム（比較例１
０）を用いた他は実施例４と同様に行った。結果を表−
２および表−３に示す。<Comparative Example 4> The same operation as in Example 10 was carried out except that the atrium sulfate was not sprayed. The results are shown in Tables 2 and 3. <Comparative Examples 5, 6 and 7> Instead of sodium chloride, magnesium sulfate (Comparative Example 5), aluminum sulfate (Comparative Example 6), and iron (II) sulfate (Comparative Example 7) were used instead of sodium chloride. Otherwise, the procedure was the same as in Example 3. Table-Results
2 and Table-3. <Comparative Examples 8, 9 and 10> As a powdering inhibitor, instead of sodium chloride, aluminum sulfate (Comparative Example 8),
Barium sulfate (Comparative Example 9), calcium sulfate (Comparative Example 1)
Except that 0) was used, the procedure was the same as in Example 4. Table-Results
2 and Table-3.
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【表２】 [Table 2]
【００３２】[0032]
【表３】 [Table 3]
【００３３】[0033]
【発明の効果】本発明によれば、これまで比重が０．１
以下の低い見かけ密度のケイ酸カルシウム成形体の有す
る問題点である粉っぽさ、すなわち手で触れた時の手ざ
わりの悪さ、粉体浮遊による作業環境の悪化などといっ
た問題を解消し、取扱性の良いケイ酸カルシウム成形体
を供給することができる。真空断熱材の芯材として用い
た場合は、真空包装時に余分な粉体が包材に付着するの
を防止できるので、シール不良による真空度の経年劣化
上昇をもたらすこともなく、高性能を長期間維持するこ
とができる。According to the present invention, the specific gravity has been 0.1%.
The following low apparent density calcium silicate compacts have the following problems: powderiness, poor touch when touched by hand, deterioration of working environment due to powder floating, etc. Calcium silicate molded body with good quality can be supplied. When used as the core material of a vacuum insulation material, excess powder can be prevented from adhering to the packaging material during vacuum packaging. Can be maintained for a period.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０４Ｂ 22:12） ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI C04B 22:12)
Claims (7)
オライトから選ばれる少なくとも１種を含むことを特徴
とする、比重が０．１以下の珪酸カルシウム成形体。1. A calcium silicate molded product having a specific gravity of 0.1 or less, characterized by containing at least one selected from alkali metal sulfates, chlorides and zeolites.
オライトから選ばれる少なくとも１種を珪酸カルシウム
１００重量部に対して５〜２０重量部含有することを特
徴とする請求項１に記載のケイ酸カルシウム成形体。2. The silicic acid according to claim 1, wherein said silicic acid contains 5 to 20 parts by weight of at least one selected from alkali metal sulfates, chlorides and zeolites based on 100 parts by weight of calcium silicate. Calcium compact.
ムであることを特徴とする請求項１または２に記載のケ
イ酸カルシウム成形体。3. The calcium silicate compact according to claim 1, wherein the alkali metal is sodium or potassium.
オライトから選ばれる少なくとも１種を含む水性液を、
ケイ酸カルシウム成形体の表面に塗布、散布もしくは含
浸して得られる請求項１ないし３いずれか１項に記載の
ケイ酸カルシウム成形体。4. An aqueous liquid containing at least one selected from alkali metal sulfates, chlorides and zeolites,
The calcium silicate molded product according to any one of claims 1 to 3, which is obtained by applying, spraying, or impregnating the surface of the calcium silicate molded product.
オライトから選ばれる少なくとも１種をケイ酸カルシウ
ムスラリーに添加した後、成形して得られる請求項１な
いし３いずれか１項に記載のケイ酸カルシウム成形体。5. The silicic acid according to claim 1, which is obtained by adding at least one selected from alkali metal sulfates, chlorides and zeolites to a calcium silicate slurry and then molding. Calcium compact.
オライトから選ばれる少なくとも１種をケイ酸カルシウ
ム成形体の表面に、２〜２０ｍｇ／ｃｍ2含有する請求
項４に記載のケイ酸カルシウム成形体6. alkali metal sulfate on the surface of at least one calcium silicate shaped body selected from chloride and zeolite, 2 to 20 mg / cm 2 of calcium silicate molded product according to claim 4 containing
のケイ酸カルシウム成形体を芯材とした真空断熱材。7. A vacuum heat insulating material comprising the calcium silicate molded body according to claim 1 as a core material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32520896A JPH10167799A (en) | 1996-12-05 | 1996-12-05 | Calcium silicate molding product and vacuum heat-insulating material using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32520896A JPH10167799A (en) | 1996-12-05 | 1996-12-05 | Calcium silicate molding product and vacuum heat-insulating material using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10167799A true JPH10167799A (en) | 1998-06-23 |
Family
ID=18174240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32520896A Pending JPH10167799A (en) | 1996-12-05 | 1996-12-05 | Calcium silicate molding product and vacuum heat-insulating material using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10167799A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005040664A1 (en) * | 2003-10-23 | 2005-05-06 | Matsushita Electric Industrial Co., Ltd. | Vacuum heat insulator, and refrigerating apparatus and cooling apparatus using the insulator |
| WO2006100730A1 (en) * | 2005-03-18 | 2006-09-28 | Kyosetu Corporation | Insulator and process for producing the same |
| JP2010518329A (en) * | 2007-02-02 | 2010-05-27 | インダストリアル インスレーション グループ | Pre-applied protective covering structure for pipe and block insulation |
| JP2021075439A (en) * | 2019-11-13 | 2021-05-20 | 学校法人日本大学 | Method for producing tobermorite-containing housing material, tobermorite, and tobermorite-containing housing material |
-
1996
- 1996-12-05 JP JP32520896A patent/JPH10167799A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005040664A1 (en) * | 2003-10-23 | 2005-05-06 | Matsushita Electric Industrial Co., Ltd. | Vacuum heat insulator, and refrigerating apparatus and cooling apparatus using the insulator |
| JP2005127409A (en) * | 2003-10-23 | 2005-05-19 | Matsushita Electric Ind Co Ltd | Vacuum heat insulation material, freezing device and cooling-warming device using vacuum heat insulation material |
| CN100383453C (en) * | 2003-10-23 | 2008-04-23 | 松下电器产业株式会社 | Vacuum heat insulator, and refrigerating apparatus and cooling apparatus using the insulator |
| WO2006100730A1 (en) * | 2005-03-18 | 2006-09-28 | Kyosetu Corporation | Insulator and process for producing the same |
| JP2010518329A (en) * | 2007-02-02 | 2010-05-27 | インダストリアル インスレーション グループ | Pre-applied protective covering structure for pipe and block insulation |
| JP2021075439A (en) * | 2019-11-13 | 2021-05-20 | 学校法人日本大学 | Method for producing tobermorite-containing housing material, tobermorite, and tobermorite-containing housing material |
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