JPS61155242A - Water-resistant fluoric anhydrous gypsum composition - Google Patents
Water-resistant fluoric anhydrous gypsum compositionInfo
- Publication number
- JPS61155242A JPS61155242A JP28094784A JP28094784A JPS61155242A JP S61155242 A JPS61155242 A JP S61155242A JP 28094784 A JP28094784 A JP 28094784A JP 28094784 A JP28094784 A JP 28094784A JP S61155242 A JPS61155242 A JP S61155242A
- Authority
- JP
- Japan
- Prior art keywords
- water
- gypsum
- weight
- water resistance
- present
- 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
- 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
- C04B28/14—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 calcium sulfate cements
- C04B28/16—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 calcium sulfate cements containing anhydrite, e.g. Keene's cement
- C04B28/165—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 calcium sulfate cements containing anhydrite, e.g. Keene's cement containing synthetic anhydrite
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、各種コンクリート構造物の外壁建築材料とし
て好適な耐水性フッ酸無水石膏組成物に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a water-resistant hydrofluoric anhydride composition suitable as an exterior wall construction material for various concrete structures.
しｆ来の技術１
鉄筋（鉄骨）コンクリート、プレキャストコンクリート
、軽量コンクリート、気泡コンクリート（ＡＬＣ）ある
いはコンクリートブロック等のコンクリート構造物にお
いては、現在、耐水性の心安とされる外壁面にはセメン
トモルタルを２０〜３０＋ｍ厚塗りして仕上げる例が多
い。しかし、このセメントモルタル塗りによると、材料
の収縮性に起因して亀裂事故や剥離事故を発生し易いと
いう不都合な点がある。Traditional technology 1 For concrete structures such as reinforced concrete, precast concrete, lightweight concrete, aerated concrete (ALC), or concrete blocks, cement mortar is currently used on the outer wall surface to ensure water resistance. In many cases, the finish is coated 20-30+m thick. However, this cement mortar coating has the disadvantage that cracking and peeling accidents are likely to occur due to the shrinkability of the material.
これに対して、石膏系の材料は無収縮性で寸法変化が少
なくクラック等の発生防止の観点からは外壁材料として
有望であるが、反面耐水性に劣るという致命的な欠点が
あり、このため従来は水が当らない内壁の場所などに限
定的に使用されているにすぎない。そこで、石膏のもつ
特徴を活しながらその耐水性に劣る点を改善するための
試みが種々提案されているが、いずれも十分なものとは
いえず、未だ石膏を主成分とする組成物をこの種外壁材
料に利用するまでには到っていない現状にある。On the other hand, gypsum-based materials are promising as exterior wall materials because they are non-shrinkable, have little dimensional change, and prevent the occurrence of cracks, etc. However, on the other hand, they have the fatal drawback of being inferior in water resistance. Conventionally, it has only been used in limited areas such as areas on interior walls that are not exposed to water. Therefore, various attempts have been proposed to take advantage of the characteristics of gypsum while improving its poor water resistance, but none of them can be said to be satisfactory, and compositions containing gypsum as the main component are still being used. At present, it has not yet been used for this type of exterior wall material.
従来の改善策について具体的に説明すると、まずα型半
水石膏、β型半水石膏及び焼石膏に耐水性を付与する［
１的で提案ｙれている方法としては、大別して次のよう
なものがある。To explain the conventional improvement measures in detail, first, water resistance is imparted to α-type hemihydrate gypsum, β-type hemihydrate gypsum, and calcined gypsum [
The first proposed methods can be roughly divided into the following.
ａ）メラミン樹脂、尿素樹脂、ビニルアルコール樹脂、
エポキシ樹脂、シリコン樹脂、ユリア樹脂、アスファル
トワックスエマルジョンなどの合成樹脂を用いて混練成
形法又は含浸法により石膏と複合化する方法。a) Melamine resin, urea resin, vinyl alcohol resin,
A method in which synthetic resins such as epoxy resins, silicone resins, urea resins, and asphalt wax emulsions are combined with plaster by kneading and molding methods or impregnation methods.
ｂ）ケイ酸ソーダ及びケイ酸カリウムなどのケイ酸アル
カリ金属塩を石膏硬化体に塗布又は含浸させる方法。b) A method of applying or impregnating a gypsum hardened body with an alkali metal silicate salt such as sodium silicate and potassium silicate.
Ｃ）ポルトランドセメント又は石灰系材料を石膏に混入
して硬化せしめる方法。C) A method in which Portland cement or lime-based materials are mixed into plaster and allowed to harden.
しかし乍ら、」−記ａ）の合成樹脂と複合化する方法で
は、触媒の混入もしくは硬化後加熱を必要とするなど、
建築材料特に左官材料としては応用できない要素を含む
不具合な点があり、また−１−記ｂ）、ｃ）のものを含
めて、いずれの方法によっても数ケ月程度の短期材令で
の耐水性は改良できても数年程度の長期材令における耐
水性を改良するまでには到らず、結局これらの方法によ
っては石膏を外壁用建築材料として使用することは困難
である。However, the method of compounding with synthetic resin described in item a) requires mixing of a catalyst or heating after curing, etc.
There are disadvantages including elements that cannot be applied as building materials, especially plastering materials, and water resistance in a short period of about several months is not achieved by any method, including those described in -1-b) and c). Even if they can be improved, it is not possible to improve the water resistance over a long period of several years, and it is ultimately difficult to use gypsum as a building material for exterior walls depending on these methods.
次に、■■型無水石膏については、焼成温度によってそ
の水和反応性が異なり、低温焼成では水利率が高いが、
高温焼成になる程水和率が低下するものである。通常、
ＴＩ型無水石膏は３００〜８００℃の温度で焼成され、
そのままでは水和反応性がきわめて低いか、Ｍ酸アルカ
リ金属ＩＩＩ等の硬化促進剤の屹加によって水利反応性
を高めることができる。しかし、水和して生成する三水
石膏に耐水性が無い点は半水石膏の場合と同様であり、
やはり前記ａ）の合成樹脂と複合化する方法又は前記ｂ
）のケイ酸アルカリ金属塩の使用等によって短期材令で
の耐水性を付与−することができても、ｋＣ期材令での
耐水性は得られず、外壁用建築材料としての使用に適さ
ないことに変りない。Next, regarding ■■ type anhydrite, its hydration reactivity differs depending on the firing temperature, and the water efficiency is high when fired at low temperatures, but
The higher the firing temperature, the lower the hydration rate. usually,
TI type anhydrite is calcined at a temperature of 300-800℃,
The hydration reactivity is extremely low as it is, or the water reactivity can be increased by adding a curing accelerator such as an alkali metal III M acid. However, similar to the case of hemihydrate gypsum, the trihydrate produced by hydration has no water resistance.
Again, the method of compounding with a synthetic resin as described in a) above or the method as described in b)
) Even if it is possible to impart water resistance in the short-term material age by using an alkali metal silicate salt, etc., water resistance in the kC period cannot be obtained, making it unsuitable for use as a building material for exterior walls. It doesn't change the fact that there isn't one.
Ｉ発明が解決しようとする問題点］
本発明は、かかる従来の技術背景に着［１してなされた
もので、コンクリート構造物の外壁建築材料に必要とさ
れる耐水性、低収縮性等の諸性質を兼備し、この種用途
に好適に使用できる石膏をに成分とした新規な耐水性フ
ッ酸無水石膏組成物を提供することを目的とするもので
ある。Problems to be Solved by the Invention] The present invention has been made based on the above conventional technical background, and has been made to solve the problems such as water resistance and low shrinkage required for external wall construction materials of concrete structures. The object of the present invention is to provide a new water-resistant hydrofluoric anhydride composition containing gypsum as a component, which has various properties and can be suitably used for this type of application.
Ｅ問題点を解決するための手段］
本発明は、このような独自の目的を実現するために研究
を重ねた結果、硫酸ナトリウム、硫酸カリウム及び硫酸
アルミニウムなどの硫酸塩からなる群から選ばれた一種
以上の硬化促進剤と水酸化カルシウムとを配合したフッ
酸無水石膏９０〜５０重量部と、高炉水滓スラグ粉末１
０〜５０重量部と、カルシウムシリケートを主成分とす
る粉末即ち、水硬性をもつカルシウムシルケートにカル
シウムアルミネート及びカルシウムアルミノフェライト
量部とを混合してなることを特徴とする、耐水性その他
の性質に優れたフッ酸無水石膏組成物を提供することが
できたものである。Means for Solving Problem E] As a result of repeated research in order to achieve this unique purpose, the present invention has developed a method using sulfates selected from the group consisting of sulfates such as sodium sulfate, potassium sulfate, and aluminum sulfate. 90 to 50 parts by weight of hydrofluoric anhydride mixed with one or more hardening accelerators and calcium hydroxide, and 1 part by weight of blast furnace water slag powder
0 to 50 parts by weight, powder mainly composed of calcium silicate, that is, calcium silicate having hydraulic properties, mixed with parts of calcium aluminate and calcium aluminoferrite, and has water resistance and other properties. It was possible to provide a hydrofluoric anhydride composition with excellent properties.
本発明に係る組成物の主成分は、フッ酸無水石膏である
。このフッ酸無水石膏は、フッ化カルシウム（螢石）と
！＆酸によりフッ化水素酸を製造する際に副生ずる無水
石膏で、結晶学的には■型無水石膏に属する。他に■型
無水石膏に属するものとして、天然無水石膏や加圧釜中
で可溶性無水石膏をさらに１悦水し結晶化した無水石膏
及び空気中３００〜８００℃の高温で焼成される無水石
膏などがある。フッ酸無水石膏は、これらの無水石膏と
結晶子の大きさ、水利速度、さらに水和して生成する三
水石膏の結晶状態などが異なる。すなわち、前述の無水
石膏の結晶子が２４０〜４００Ａであるのに対して，フ
ッ酸無水石膏の結晶子は５００〜６５０Ａで、これは１
０００〜１１００℃で焼成される無水石膏の結晶子に
相当する。フッ酸無水石膏が２００〜３５０℃の反応キ
ルン中で生成する無水石膏にもかかわらず、このように
大きな結晶子をとる理由は、フッ酸無水石膏が特定な化
学反応によって直接合成される無水石膏であるからと考
えられる。The main component of the composition according to the present invention is hydrofluoric anhydride. This hydrofluoric anhydride is calcium fluoride (fluorite)! It is an anhydrite that is produced as a by-product when producing hydrofluoric acid using an acid, and belongs to the type ■ anhydrite crystallographically. Other types of anhydrite include natural anhydrite, anhydrite crystallized by further hydrating soluble anhydrite in a pressure cooker, and anhydrite calcined in air at a high temperature of 300 to 800°C. be. Hydrofluoric anhydride differs from these anhydrites in terms of crystallite size, water utilization rate, and crystalline state of trihydrate produced by hydration. That is, while the crystallites of the aforementioned anhydrite are 240 to 400A, the crystallites of hydrofluoric anhydride are 500 to 650A, which is 1
It corresponds to anhydrite crystallites calcined at 000 to 1100°C. The reason why hydrofluoric anhydride takes such large crystallites is because it is anhydrite that is synthesized directly through a specific chemical reaction, even though it is anhydrite that is produced in a reaction kiln at 200 to 350°C. This is thought to be because.
一般に半水石膏は水和速度が〒−〈生成する三水石膏は
ほとんど針状結晶をとるのに対して、■型無水石膏は水
利速度が遅く生成する三水石膏は針状結晶と柱状結晶を
とる。さらにＩＩ型無水石膏についていえば、焼成温度
が高くなるほど結晶子が大きくなり水和速１Ｗが緩慢に
なる。そして、生成する工水石膏には柱状結晶が占める
割合が多くなり高強度で重い容重をしめず硬化体が得ら
れる。In general, gypsum hemihydrate has a hydration rate of 〒-〒< most of the produced trihydrate forms needle-shaped crystals, whereas ■-type anhydrite forms at a slow rate of water utilization.Trihydrate produces needle-shaped crystals and columnar crystals. Take. Furthermore, regarding type II anhydrite, the higher the firing temperature, the larger the crystallites and the slower the hydration rate 1W. Then, the ratio of columnar crystals in the generated industrial water gypsum increases, and a hardened product with high strength and low weight can be obtained.
本発明で、フッ酸無水石膏を用いる主な必要性は、まさ
しくこれらの点にある。すなわちフッ酸素水石膏はｎ型
無水石膏の中でも特に結晶子が大きく、水和速度が遅く
、生成する工水石膏に柱状結晶が多いという特徴をもつ
。工業的な副産石膏で本発明の目的とする物性が得られ
るものは、現在のところフッ酸無水石膏のみのようであ
る。もちろん工水石膏を焼成して本発明の目的とする物
性をもつ無水石膏を製造できるが、それには前述したよ
うに１０００〜ｔｔｏｏ℃の高温焼成を必要とし、本発
明組成物の用途上、経済的に見合わないものとなる。The main necessity of using hydrofluoric anhydride in the present invention lies precisely in these points. In other words, fluoroxygen aqueous gypsum has particularly large crystallites among n-type anhydrite, has a slow hydration rate, and has many columnar crystals in the produced aqueous gypsum. At present, hydrofluoric anhydride appears to be the only industrial gypsum that can provide the physical properties targeted by the present invention. Of course, anhydrous gypsum having the physical properties targeted by the present invention can be produced by firing industrial gypsum, but as mentioned above, this requires high-temperature firing of 1000 to 100°C, which makes it economically difficult to use the composition of the present invention. It becomes unreasonable.
以下の説明及び図表中で焼成無水石膏と呼称するものは
、工水石膏を、代表的な焼成温度である５００℃で１時
間焼成して調整したものである。What is referred to as calcined anhydrite in the following description and diagrams is prepared by calcining industrial gypsum at a typical firing temperature of 500° C. for 1 hour.
このような温度で焼成された無水石膏とフッ酸無水石膏
は、いずれも結晶学的にはｎ型無水石膏に属するが、結
晶子の大きさ、水和速度及び生成する工水石膏の結晶状
態などにおいて性質が異なるものである。Both anhydrite and hydrofluoric anhydrite calcined at such temperatures belong to n-type anhydrite in terms of crystallography, but the size of crystallites, hydration rate, and crystalline state of the produced gypsum They have different properties, such as:
本発明に係る組成物は、硬化促進剤として硫酸ナトリウ
ム、硫酸カリウム及び硫酸アルミニウムなどの硫酸塩か
らなる群から選ばれた一種以上と中和剤として水酸化カ
ルシウムを配合した上記のフッ酸無水石膏９０〜５０重
早一部に、高炉水滓スラグ粉末１０〜５０重量部を混合
して、その硬化体の耐水性を付与している。このさい、
高炉水滓スラグ粉末の混合量の増加に伴ない耐水性は向
上し１例えばフッ酸無水石膏５０重量部に高炉水滓スラ
グ粉末５０重量部を混合してなる硬化体では、流水中養
生で約３ケ月まで耐水性を示すが、それ以上の長期材令
での耐水性は無く、重量減少及び強度低Ｆを招く。The composition according to the present invention comprises the above-mentioned hydrofluoric anhydride containing one or more selected from the group consisting of sulfates such as sodium sulfate, potassium sulfate and aluminum sulfate as a hardening accelerator and calcium hydroxide as a neutralizing agent. 10 to 50 parts by weight of blast furnace water slag powder is mixed with 90 to 50 parts by weight to impart water resistance to the hardened product. At this time,
Water resistance improves as the amount of blast furnace slag powder increases.1For example, in a hardened product made by mixing 50 parts by weight of hydrofluoric acid anhydride with 50 parts by weight of blast furnace slag powder, curing in running water increases the water resistance. Although it exhibits water resistance for up to 3 months, it has no water resistance for longer than that, resulting in weight loss and low strength F.
さらに、本発明に係る組成物は、−上記フッ酸無水石膏
９０〜５０重量部と高炉水５室スラグ粉末１θ〜５０市
酸部と混合したものに、水硬性をもつカルシウムシリケ
ートにカルシウムアルミネート及びカルシウムアルミノ
フェライトを含むか含まない粉末３０〜１００重輌部を
混合して、長期材令でも良好な耐水性を示す、即ち、流
水中養生２年経過後においても硬化体の重量減少や強度
低下を示さないものを提供する。カルシウムシリケート
を主成分とする粉末は、３０重垂部以下では本発明の目
的とする耐水性が得られず、また１００重量部以上では
長さ変化が大きくなり不都合をきたす。本発明で使用す
るカルシウムシリケート、カルシウムアルミネート及び
カルシウムアルミノフェライトは紬薬合成したものでも
よいし、ポルトランドセメントや超速硬性セメント（商
品名ライオンシスイ＄１０１、＃１０５、＃１１５、＃
１６０）などの混合粉末でもよい。また、これらカルシ
ウムシリケート化合物には、高炉セメント（普通ポルト
ランドセメントにスラグ粉末を配合したもの）も一種と
して含まれる。Furthermore, the composition according to the present invention includes: - a mixture of 90 to 50 parts by weight of the above-mentioned hydrofluoric anhydride and 1θ to 50 parts by weight of blast furnace water 5-chamber slag powder, calcium silicate having hydraulic properties, and calcium aluminate; By mixing 30 to 100 parts of powder containing or not containing calcium aluminoferrite, it shows good water resistance even after long-term aging, that is, even after 2 years of curing in running water, there is no weight loss or strength of the cured product. Provide something that does not show any decline. If the powder containing calcium silicate as a main component is less than 30 parts by weight, the water resistance that is the object of the present invention cannot be obtained, and if it is more than 100 parts by weight, the change in length becomes large, causing problems. Calcium silicate, calcium aluminate, and calcium aluminoferrite used in the present invention may be those synthesized by pongee medicine, or may be made of Portland cement or ultra-fast hardening cement (trade name: Lion Sisui $101, #105, #115, #
A mixed powder such as 160) may also be used. These calcium silicate compounds also include blast furnace cement (ordinary Portland cement mixed with slag powder).
酸物では、
ｌ）流水中養生あるいは乾湿繰り返し養生の長期材令に
おいても、重量減少及び強度低下がない、２）乾燥収縮
が少なく、亀裂事故や剥離事故が発生しない、
３）凝結時間及び強度発現等の物性の温度依存性が少な
く、５℃前後の低温から３５℃前後の高温にわたって安
定した物性が得られる、
４）石膏系建築材料の塗布工事で発生する錆が発生しな
いなど、
耐水性、収縮性、温度依存性及び防錆性のすべての面で
優れた性質を兼備できるものとなっている。For acid materials, 1) There is no weight loss or strength loss even after long-term aging by curing in running water or repeated wet and dry curing, 2) There is little drying shrinkage and no cracking or peeling accidents occur, 3) Setting time and strength There is little temperature dependence of physical properties such as development, and stable physical properties can be obtained from low temperatures of around 5 degrees Celsius to high temperatures of around 35 degrees Celsius. 4) Water resistance, such as no rust that occurs when applying plaster-based building materials. It has excellent properties in all aspects: shrinkage, temperature dependence, and rust prevention.
本発明のフッ酸無水石膏組成物には、混和材として、エ
チレン酢酸ビニル樹脂、アクリル酸エステル樹脂及びス
チレンブタジェン合成ゴム樹脂の一種以上を、固形物換
算で１〜３０重量部添加することができる。これらの合
成樹脂は防水皮膜を形成することにより、本発明組成物
の添加は、耐−Ｊｅ Ｍｈ も ！ 仁、 ＋＋
＋ ｔ＝１ Ｌ ＜ ｘ ｘ Ｍ ＋ｗ
４ ｍ ｉ ＋ ＊ ＋ Ｊ＋
ｘち、１重に部具下では本発明の基本組成物量」二の耐
水性を付与する効果がなく、また３０重＠部以−Ｌでは
作業性に劣４Ｊ ８９塗りが困難となり、さらに強度低
Ｆを招くためである。そして、耐火性能及び価格の−１
−からの好ましくない。The hydrofluoric anhydride composition of the present invention may contain, as an admixture, 1 to 30 parts by weight of one or more of ethylene vinyl acetate resin, acrylic ester resin, and styrene butadiene synthetic rubber resin in terms of solid matter. can. Since these synthetic resins form a waterproof film, the addition of the composition of the present invention also provides resistance to -JeMh! Jin, ++
+ t=1 L < x x M +w
4 m i + * + J+
However, if the basic composition of the present invention is used in one layer, it will not have the effect of imparting water resistance, and if it is 30 layers or more, the workability will be poor, and coating will be difficult, and the strength will be increased. This is to cause low F. And -1 in fire resistance performance and price
- Unfavorable from.
本発明のフッ酸無水石膏組成物には、また、シロキサン
のオリゴマーを主成分とするシリコン樹脂を０．５〜５
．０重酸部添加することができる。このシリコン樹脂の
添加は撓水性の付与−を１−１的とするものである。す
なわち、０．５垂訓部以ドでは本発明の基本組成物量−
１−の耐水性付与の効果がなく、また５、０重酸部以−
Ｉ−では泥水」直の増加に伴い強度低ドを招き好ましく
ないからである。The hydrofluoric anhydride composition of the present invention also contains 0.5 to 5% of a silicone resin whose main component is a siloxane oligomer.
．． 0 parts of heavy acid can be added. The addition of this silicone resin provides water repellency in a 1-1 manner. That is, from 0.5 sermons onwards, the basic composition amount of the present invention -
1- has no effect of imparting water resistance, and more than 5,0 parts of heavy acid
This is because in case of I-, the strength decreases due to the increase in muddy water, which is undesirable.
さらに、本発明のフッ酸無水石膏組成物には、大豆油、
ヒマワリ油、ナタネ油、米ぬか油、ゴム油、ヤシ油、パ
ーム油、オリーブ油あるいはヒマシ油等の植物油の一種
以上を１〜３０重礒部添加することもできる。この植物
油の添加はシリコン樹脂と同様に幣水性の付手を目的と
するものである。すなわち、１重酸部より少ないと耐水
性に対して本発明の基本組成物以上の改善効果が期待で
きず、一方３０屯量部以上では作業性に劣り鰻塗りが困
難となり、又強度低下を招くからである。Furthermore, the hydrofluoric anhydride composition of the present invention includes soybean oil,
It is also possible to add 1 to 30 weight parts of one or more vegetable oils such as sunflower oil, rapeseed oil, rice bran oil, rubber oil, coconut oil, palm oil, olive oil, or castor oil. The purpose of adding this vegetable oil is to make it water-resistant, similar to the silicone resin. That is, if the amount is less than 1 part by weight, no improvement in water resistance can be expected than that of the basic composition of the present invention, while if it is more than 30 parts by weight, the workability is poor, making it difficult to coat the eel, and the strength may decrease. Because it invites you.
本発明のフッ酸無水石膏組成物は、その優れた耐水性か
らセメントモルタルと同様に各種コンクリート構造物の
外望用建築材料として使用できる。そして、この組成物
による壁面施工では、必要な外壁面に１０１１１１１以
下の塗厚で塗布すれば足りるものである。なお、骨材を
混合して石膏モルタルとして使用する場合では、川砂、
山砂、海砂、珪砂、寒水石、砕石、焼成黒よう石、焼成
真珠岩あるいは焼成蛭石の一種以上を容積比で０．５〜
４倍量加えて用いればよい。Due to its excellent water resistance, the hydrofluoric anhydride composition of the present invention can be used as a building material for the exterior of various concrete structures, similar to cement mortar. When applying this composition to a wall surface, it is sufficient to apply it to the required outer wall surface with a coating thickness of 1011111 or less. In addition, when mixing aggregate and using it as gypsum mortar, river sand,
One or more types of mountain sand, sea sand, silica sand, kansui stone, crushed stone, calcined melanite, calcined pearlite, or calcined vermiculite at a volume ratio of 0.5 to
It may be used by adding four times the amount.
し作用」
耐水性
フッ酸無水石膏９０〜５０重量部と高炉水滓スラグ粉末
１０〜５ Ｑ ｑ＜ ｆＪ部とに、前記のカルシウムシ
ルケートを主成分とする粉末を３０〜１００重騎部混合
せしめることにより、流水中養生３年経過までの実試の
結果並びにその水和物の電子類微鏡観察の結果から、本
発明のフッ酸無水石膏組成物では半永久的な耐水性を具
備するものと推測される。すなわち、若水又は無水石膏
の水和時にカルシウムシリケートが共存すると、
■）耐水性のあるカルシウムシリケート永和物が耐水性
のない工水石膏の表面を被覆すること、および、
２）工水石膏とカルシウムシリケートが反応してカルシ
ウムシリケート・石膏水和物が三水石膏表面に析出する
こと、
により耐水性が付与される。以上の作用により石膏に耐
水性が付与される場合、比表面積の少ない柱状結晶を多
く生成するフッ酸無水石膏の方が少ないカルシウムシリ
ケートでより効果的に耐水性が向−ヒする。実際に本発
明組成物のうちフッ酸無水石膏を半水石膏などでおきか
えると、少しの耐水性は打手されるが、本発明組成物は
どの耐水性には至らず、流水中１年で強度低ｆを招く。30 to 100 parts by weight of the above-mentioned calcium silicate-based powder is mixed with 90 to 50 parts by weight of water-resistant hydrofluoric anhydride and 10 to 5 parts by weight of blast furnace water slag powder. As a result, the hydrofluoric anhydride composition of the present invention has semi-permanent water resistance, based on the results of actual trials up to three years after curing in running water and the results of electron microscope observation of the hydrate. It is assumed that. That is, if calcium silicate coexists during the hydration of young water or anhydrite, 1) the water-resistant calcium silicate permanent coats the surface of non-water-resistant aqueous gypsum, and 2) the relationship between aqueous gypsum and calcium. Silicates react and calcium silicate/gypsum hydrate precipitates on the surface of trihydrate, giving it water resistance. When water resistance is imparted to gypsum by the above-mentioned effects, water resistance is improved more effectively with hydrofluoric anhydride gypsum, which forms many columnar crystals with a small specific surface area, with less calcium silicate. In fact, if hydrofluoric anhydride in the composition of the present invention is replaced with gypsum hemihydrate, etc., a slight degree of water resistance can be achieved, but the composition of the present invention does not reach any level of water resistance, and has strength after one year under running water. This results in low f.
半水石膏に本発明組成物と同等の耐水性を付与する′
Ｌデ ｌ−） ４ｂ 堂Ｌ４
うら ｌ の 六 １１７・ソ ウ ム ・ソ １１
、ケ − ト か Ａソ、弾とし、石膏の長所である
寸法安定性が著しく低下し乾燥収縮の大きい効果体しか
得られなくなる。To impart water resistance to hemihydrate gypsum equivalent to that of the composition of the present invention'
L de l-) 4b hall L4
Back l no 6 117・Soum・So 11
If it is used as a bullet, the dimensional stability, which is an advantage of plaster, will be significantly reduced, and only the effect of large drying shrinkage will be obtained.
収縮性
カルシウムシリケート、カルシウムアルミネート及びカ
ルシウムアルミノフェライトは、いずれの粉末も水硬性
を有し、硬化後硬化体に含まれる微細な毛細管の中の水
分蒸発し、このとき張力が生じて収縮を示す。特に、カ
ルシウムアルミネート及びカルシウムシリケートの乾燥
収縮は大きい。しかし、本発明のフッ酸無水石膏組成物
では、フッ酸無水石膏と高炉水滓スラグ粉末中に含まれ
るアルミナ分との水和反応及びフッ酸無水石膏とカルシ
ウムアルミネートとの水和反応により生成するエトリン
ガイト ［（Ｅ、Ａ・３ＣａＳＯ４・３２Ｈ２０］の膨
張性によって収縮が抑制されるため、収縮はきわめて低
い。Shrinkable calcium silicate, calcium aluminate, and calcium aluminoferrite all have hydraulic properties, and after curing, the water in the fine capillaries contained in the cured product evaporates, creating tension and causing contraction. . In particular, calcium aluminate and calcium silicate have large drying shrinkage. However, in the hydrofluoric anhydride composition of the present invention, it is produced through a hydration reaction between hydrofluoric anhydride and alumina contained in blast furnace water slag powder and a hydration reaction between hydrofluoric anhydride and calcium aluminate. The shrinkage is extremely low because the expansion property of ettringite [(E, A.3CaSO4.32H20) suppresses the shrinkage.
温度依存性
フッ酸無水石膏は低温程水利反応性が高く、硬化が早く
て強度発現に優れ、逆に高温になる程水和反応性が低下
し、硬化が遅れて強度発現も悪くなる。一方、高炉木膣
スラク粉末やカルシウムシリケート、カルシウムアルミ
ネート及びカルシウムアルミノフェライトの各粉末は高
温での水和反応性に富み、硬化及び強度発現に良好であ
るが、逆に低温では硬化が遅れ強度発現も悪くなる。本
発明のフッ酸無水石膏組成物は、これらの成分の混合物
であって、互いにその水和硬化性を補うことにより、前
述のように、５℃前後の低温から３“５℃前後の高温に
わたって安定した物性が得られるものである。Temperature-dependent hydrofluoric anhydride has higher water reactivity at lower temperatures, hardens more quickly, and exhibits better strength; conversely, the higher the temperature, the lower its hydration reactivity, the slower it hardens, and the worse it develops strength. On the other hand, blast furnace wood slurry powder, calcium silicate, calcium aluminate, and calcium aluminoferrite powders have high hydration reactivity at high temperatures and are good for hardening and strength development, but on the other hand, hardening is delayed at low temperatures and strength increases. Expression also worsens. The hydrofluoric anhydride composition of the present invention is a mixture of these components, and by mutually supplementing their hydration hardenability, the hydrofluoric anhydride composition of the present invention can be cured from a low temperature of around 5°C to a high temperature of around 35°C, as described above. Stable physical properties can be obtained.
防錆性
建築用左官材料として使用される石膏は殆ど副生化学石
膏であり、残留する酸性物質を含む場合が多い０石膏は
化学的に中性であり、消石灰やドロマイトをまぜて使用
することもあるが、その場合でも塗布後の中性化はきわ
めて早い、鉄はｐ旧０以−Ｌのアルカリ領域で不動態化
し、空気と水分カー存在しても錆を発生しないが、中性
から酸性領域では空気と水分の存在下で発錆する。そし
て、石膏系左官材料の塗布工事では、塗布材料の水分が
抜けきらないうちに中性化するために、鉄製建具と接触
する部分で錆が発生する。これに対して、本発明のフッ
酸無水石膏組成物では、カルシウムシリケート、カルシ
ウムアルミネート及びカルシウムアルミノフェライトが
水和して一部水酸化カルシウムを生成する。この水酸化
カルシウムは、ＰＨ１２以上の強アルカリ性で、鉄を不
動態化させ錆の発生を抑制する効果がある。Most of the gypsum used as rust-proof architectural plastering material is by-product chemical gypsum, and it often contains residual acidic substances.Gypsum is chemically neutral and can be used by mixing it with slaked lime or dolomite. However, even in that case, the neutralization after coating is extremely quick. Iron becomes passivated in the alkaline region of p<0 to -L, and does not rust even in the presence of air and moisture. Rust occurs in the presence of air and moisture in acidic areas. When applying gypsum-based plastering materials, rust occurs in the parts that come into contact with iron fittings because the material neutralizes before the water is completely removed. In contrast, in the hydrofluoric anhydride composition of the present invention, calcium silicate, calcium aluminate, and calcium aluminoferrite are hydrated to partially produce calcium hydroxide. This calcium hydroxide is strongly alkaline with a pH of 12 or higher, and has the effect of passivating iron and suppressing the formation of rust.
［実施例］
以下、本発明の実施例を比較例とともに末尾の表に掲げ
、本発明に係るフッ酸無水石膏組成物の優れた性質を明
らかにする。[Examples] Examples of the present invention are listed below along with comparative examples in the table at the end to clarify the excellent properties of the hydrofluoric anhydride composition according to the present invention.
ここに、第１表は試験に供した各種石膏系材料の成分配
合を示し、第２表は長期材令での耐水性に関する試験結
果を、第３表は同じく寸法安定性に関する試験結果を、
また第４表は温度依存性にに関する試験結果を示してい
る。Here, Table 1 shows the composition of various gypsum-based materials subjected to the test, Table 2 shows the test results regarding water resistance in long-term material age, and Table 3 shows the test results regarding dimensional stability.
Table 4 also shows test results regarding temperature dependence.
なお、試験は本発明組成物に対し、重量比で２゜５倍量
の乾燥珪砂（２，５ｍｍフルイ下）を骨材として使用し
、混水酸はＪＩＳ Ｒ５２０１のフロー試験方法に準じ
てフロー（ｆｉ１８０±３ｍｍとなるように調節して各
供試体を作製したものである。各試験の内容を説明する
と、まず第４表における凝結試験はＪＩＳＲ５２０１お
よびＪＩＳ Ａ３９０４に準じてビガー針装置を用いて
凝結時間を測定した。なお、気温５℃、２０℃及び３５
℃の３条件下で行な′っている。また、第２表及び第４
表における気中圧縮強度試験はＪＩＳＲ５２０１に準じ
て測定したものである。この場合、その供試体寸法は４
Ｘ４Ｘ１６ｃｍとし、打込後翌日脱型して所定材令まで
気′！！５℃、２０℃及び３５℃の３条件下で養生した
。また、第３表における長さ変化率はＪＩＳ Ａ１１２
１３のコンパレーター法に準じて測定した。そして、や
はり供試体寸法は４×４×１６ｃ■とし、打込後翌日説
型して店長を測定し、気温２０℃湿度８０ＸＲＨの雰囲
気下で養生して長さ変化率を測定した。さらに、第２表
における流水中型に変化及び流水生圧縮強度については
、耐水性に関する公的規格がないため次のようにした。In addition, in the test, dry silica sand (under a 2.5 mm sieve) in an amount of 2.5 times the weight of the composition of the present invention was used as the aggregate, and the mixed acid was subjected to a flow test according to the flow test method of JIS R5201. (Each specimen was prepared by adjusting the fi 180 ± 3 mm. To explain the contents of each test, first, the condensation test in Table 4 was conducted using a Vigor needle device according to JISR5201 and JIS A3904. The condensation time was measured at temperatures of 5°C, 20°C and 35°C.
The experiments were carried out under three conditions: ℃. Also, Table 2 and 4
The air compressive strength test in the table was measured according to JISR5201. In this case, the specimen size is 4
X4X16cm, remove the mold the next day after driving, and heat until the specified material age! ! It was cured under three conditions: 5°C, 20°C and 35°C. In addition, the length change rate in Table 3 is JIS A112
It was measured according to the comparator method of No. 13. The dimensions of the specimen were 4 x 4 x 16 cm, and the mold was molded the next day after casting, and the length change rate was measured after curing in an atmosphere of 20°C and 80xRH. Furthermore, the change in flowing type and the flowing compressive strength in Table 2 were determined as follows since there is no official standard regarding water resistance.
すなわち、ここでは縦２．１＊Ｘ横０．８曹×深さ０．
４腸にに士 １４．し感色り＾蛸＾肩伯吻出１ず嬰磐
を曽１＋Ｆ １ζイブをはわせてＩＱａｍ間隔に穴
をあけそこから流水量を５００ｍ ｌ ／ｗｉｎに調節
しつつ水道水を流入させ上部から過剰水をオーバーフロ
ーさせる流水条件下に４Ｘ４Ｘ１６ｃｍの供試体を養生
し、その重量変化測定し、またＪＩＳ Ｒ５２０１に準
じて圧縮強度を測定するようにしている。そして、第２
表における乾湿繰り返し養生の圧縮強度については、上
述の流水中１６時間、気温２０℃の気中８時間の繰り返
し条件ｒで養生した４Ｘ４Ｘ１６ｃｍの供試体の圧縮強
度をＪＩＳｔ Ｒ５２０１に準じて測定したものである
。That is, here, the length is 2.1*X the width is 0.8mm*The depth is 0.
4. Intestines 14. A feeling of color ＾Octopus＾Shoulder and proboscis 1zukoiwa
A 4 x 4 x 16 cm specimen was cured under running water conditions, with tap water flowing in while adjusting the water flow rate to 500 ml/win, and excess water overflowing from the top. Then, the weight change is measured, and the compressive strength is measured according to JIS R5201. And the second
Regarding the compressive strength after repeated wet-dry curing in the table, the compressive strength of a 4 x 4 x 16 cm specimen cured under the above-mentioned repeated conditions r of 16 hours in running water and 8 hours in air at a temperature of 20°C was measured in accordance with JISt R5201. be.
この実施例の結果から理解されるように、本発明に係る
ものでは、他種の石膏系材料に比較すると、長期材令（
２年）においても十分な耐水性が得られ、しかも寸法安
定性に優れ物性の温度依存性も少ないことが確かめられ
る。As can be understood from the results of this example, compared to other types of gypsum-based materials, the material according to the present invention has a long-term material life (
It was confirmed that sufficient water resistance was obtained even after 2 years), and that the dimensional stability was excellent and the temperature dependence of physical properties was small.
［発明の効果］
以上のように、本発明のフッ酸無水石膏組成物は１石膏
系材料の欠点であった耐水性に劣る点を長期材令にわた
り良好なものに改善することができて、耐水性 鼾りＩ
ｖ嫁騨かり＾ｐｉ、 ｓｔ ＆楕址暦↓−時に満足させ
ることができ、既述の外壁建築材料の用途に頗る好適な
ものを提供している。また、他の用途としてボード、ブ
ロック、パネルなどの成型品用材料にも利用可能である
。[Effects of the Invention] As described above, the hydrofluoric anhydride composition of the present invention can improve the poor water resistance, which was a drawback of gypsum-based materials, to one that is good over a long period of time. Water resistance Snoring I
It can satisfy the customer's needs and provides an extremely suitable material for the exterior wall construction materials mentioned above. It can also be used as a material for molded products such as boards, blocks, and panels.
Claims (1)
どの硫酸塩からなる群から選ばれた一種以上の硬化促進
剤と水酸化カルシウムとを配合したフッ酸無水石膏９０
〜５０重量部と、高炉水滓スラグ粉末１０〜５０重量部
と、カルシウムシルケートを主成分とする粉末３０〜１
００重量部とを混合してなることを特徴とする耐水性フ
ッ酸無水石膏組成物。Hydrofluoric anhydride 90 containing calcium hydroxide and one or more hardening accelerators selected from the group consisting of sulfates such as sodium sulfate, potassium sulfate and aluminum sulfate.
~50 parts by weight, 10 to 50 parts by weight of blast furnace water slag powder, and 30 to 1 part by weight of powder whose main component is calcium silicate.
1. A water-resistant hydrofluoric anhydride composition, characterized in that it is formed by mixing 00 parts by weight of hydrofluoric anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28094784A JPS61155242A (en) | 1984-12-26 | 1984-12-26 | Water-resistant fluoric anhydrous gypsum composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28094784A JPS61155242A (en) | 1984-12-26 | 1984-12-26 | Water-resistant fluoric anhydrous gypsum composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61155242A true JPS61155242A (en) | 1986-07-14 |
Family
ID=17632123
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28094784A Pending JPS61155242A (en) | 1984-12-26 | 1984-12-26 | Water-resistant fluoric anhydrous gypsum composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61155242A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6389447A (en) * | 1986-10-01 | 1988-04-20 | 三菱マテリアル株式会社 | Manufacture of fiber reinforced gypsum base hardened body |
| JPH0193450A (en) * | 1987-10-01 | 1989-04-12 | Asou Cement Kk | High-strength additive for secondary product of concrete |
| US5730496A (en) * | 1995-12-21 | 1998-03-24 | Toyota Jidosha Kabushiki Kaisha | Vehicle rear seat device |
| JP2010208870A (en) * | 2009-03-06 | 2010-09-24 | Yoshino Gypsum Co Ltd | Gypsum composition capable of restraining occurrence of hydrogen sulfide and gypsum-based building material |
| JP2011088824A (en) * | 2011-02-10 | 2011-05-06 | Yoshino Gypsum Co Ltd | Gypsum composition controllable of generation of hydrogen sulfide, gypsum-based building material, and gypsum-based solidifying material |
| CN110981259A (en) * | 2019-12-16 | 2020-04-10 | 河海大学 | Additive for improving crystallinity of hydro-thermal synthesis hydrated calcium silicate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58217455A (en) * | 1982-06-11 | 1983-12-17 | 清水建設株式会社 | Anhydrous gypsum composition for flow-spread floor material and construction therefor |
-
1984
- 1984-12-26 JP JP28094784A patent/JPS61155242A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58217455A (en) * | 1982-06-11 | 1983-12-17 | 清水建設株式会社 | Anhydrous gypsum composition for flow-spread floor material and construction therefor |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6389447A (en) * | 1986-10-01 | 1988-04-20 | 三菱マテリアル株式会社 | Manufacture of fiber reinforced gypsum base hardened body |
| JPH0242784B2 (en) * | 1986-10-01 | 1990-09-26 | ||
| JPH0193450A (en) * | 1987-10-01 | 1989-04-12 | Asou Cement Kk | High-strength additive for secondary product of concrete |
| US5730496A (en) * | 1995-12-21 | 1998-03-24 | Toyota Jidosha Kabushiki Kaisha | Vehicle rear seat device |
| JP2010208870A (en) * | 2009-03-06 | 2010-09-24 | Yoshino Gypsum Co Ltd | Gypsum composition capable of restraining occurrence of hydrogen sulfide and gypsum-based building material |
| JP2011088824A (en) * | 2011-02-10 | 2011-05-06 | Yoshino Gypsum Co Ltd | Gypsum composition controllable of generation of hydrogen sulfide, gypsum-based building material, and gypsum-based solidifying material |
| CN110981259A (en) * | 2019-12-16 | 2020-04-10 | 河海大学 | Additive for improving crystallinity of hydro-thermal synthesis hydrated calcium silicate |
| CN110981259B (en) * | 2019-12-16 | 2021-05-28 | 河海大学 | Additive for improving crystallinity of hydro-thermal synthesis hydrated calcium silicate |
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