JPH0341422B2 - - Google Patents
Info
- Publication number
- JPH0341422B2 JPH0341422B2 JP58178318A JP17831883A JPH0341422B2 JP H0341422 B2 JPH0341422 B2 JP H0341422B2 JP 58178318 A JP58178318 A JP 58178318A JP 17831883 A JP17831883 A JP 17831883A JP H0341422 B2 JPH0341422 B2 JP H0341422B2
- Authority
- JP
- Japan
- Prior art keywords
- aluminum phosphate
- water
- glass
- phosphate glass
- pot life
- 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.)
- Expired - Lifetime
Links
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 45
- 239000003795 chemical substances by application Substances 0.000 claims description 44
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 35
- 239000005365 phosphate glass Substances 0.000 claims description 33
- 235000019353 potassium silicate Nutrition 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000011282 treatment Methods 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 17
- 239000000920 calcium hydroxide Substances 0.000 description 17
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000004570 mortar (masonry) Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- -1 acetate ester Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/16—Acids or salts thereof containing phosphorus in the anion, e.g. phosphates
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Description
〔産業上の利用分野〕
本発明はケイ酸ソーダ，ケイ酸カリ等の溶液、
いわゆる水ガラスの硬化剤に関するものである。
〔従来の技術〕
水ガラスは安価で毒性もなく従来より結合剤と
して接着剤や塗料用等に広く用いられている。し
かしながら水ガラスは、そのまま風乾して硬化さ
せたような場合には、水ガラスの構成成分である
ケイ酸アルカリ自体が水溶性を示すため、非常に
耐水性の悪い硬化体となつてしまう。このため通
常ケイフツ化ソーダ、リン酸アルミニウム、縮合
リン酸アルミニウム、酢酸エステル等種々の硬化
剤が耐水性の改良や硬化時間の調整を行うために
使用されてきているが、硬化時間の長いもので
は、耐水性に劣つてしまつたりして、まだまだ満
足のいくものがないのが実状である。
例えば、水ガラスの硬化剤として一般によく知
られているケイフツ化ソーダは劇物であり、取扱
い上種々の規制を受け、使用に際しては可使時間
が短く、硬化体の耐水性もまだまだ十分とは言え
ないという欠点を有している。
また耐水性の面では比較的良好な物性を示すと
されている縮合リン酸アルミニウムについても、
製造に際し、その縮合過程を行うにあたり、特別
な製造方法を要し、なかなか煩雑になり、安価な
ものが得られにくい上に、可使時間の調整もなか
なか困難であるという欠点を有している。いずれ
にしてもそれぞれの硬化剤には、一長一短があ
り、簡単に可使時間の調整ができ、かつ耐水性の
良好なものはないというのが実状である。
〔発明が解決しようとする課題〕
そこで、本発明は、水ガラス用硬化剤として用
いた時、硬化体が良好な耐水性を示すと共に、可
使時間の調整が容易な水ガラス硬化剤を提供する
ことを目的とするものである。
〔課題を解決するための手段〕
本発明者等は上記の目的を達成するために種々
検討の結果、リン酸アルミニウムガラスが水ガラ
スの硬化剤として、縮合リン酸アルミニウムと同
様な良好な耐水性を示すという知見を得た。しか
しリン酸アルミニウムガラスそのままでは、可使
時間が短いという欠点があり、接着剤や塗料等と
して実際に使用する場合には、可使時間の長いも
のが要求される場合が多いのが実状である。そこ
でさらに種々検討の結果、リン酸アルミニウムガ
ラス粉末を、リン酸イオンと反応して、リン酸ア
ルミニウムガラス粉末粒子表面に不溶性あるいは
難溶性の塩を形成するような処理剤にて表面化学
処理したもの、例えば水酸化カルシウム懸濁液に
て表面化学処理したものを水ガラス用硬化剤とす
ると、硬化体の物性は、縮合リン酸アルミニウム
やリン酸アルミニウムガラスそのものとほとんど
変わることなく、可使時間を容易に伸ばせること
を見いだし、本発明の硬化剤としたものである。
ところでリン酸アルミニウムガラスは本質的に
は、アルミナ（Al2O3）と無水リン酸（P2O5）と
より成り、連続した−Ｏ−Al−Ｏ−Ｐ−Ｏ−結
合を有しているものとされている。
本発明の硬化剤の製造に用いるリン酸アルミニ
ウムガラスの製造には、Al2O3源としては、アル
ミナあるいは水酸化アルミニウム等が、また
P2O5源としてはリン酸やリン酸のアンモニウム
塩等が考えられるが、その他Al2O3とP2O5の化合
物であるAl2O3・P2O5やAl2O3・3P2O5等を適当
に混合調整したものを高温で溶融後急冷して製造
することが可能である。
Al2O3−P2O5系のガラス化範囲は、一般的には
Al2O3・3P2O5（Al2O319.3重量％、P2O580.7重量
％）に近い組成からAl2O3・3P2O5とAl2O3・
P2O5の共融点組成より少しAl2O3に富むAl2O330
重量％P2O570重量％程度までガラスが得られる
ことが判明している。これ以外の組成でもガラス
は得られる可能性はあるが、ガラス製造に際し
Al2O3が多くなるとP2O5の蒸発量が多くなつてし
まうというように、リン酸アルミニウムガラスの
製造が、より困難となつてしまうため、本発明の
硬化剤製造用としては、通常上記範囲内のリン酸
アルミニウムガラスで十分である。
なおリン酸アルミニウムガラスとしての本質的
な特性、例えば水やアルカリ水溶液への溶解性を
大幅に変えないものであれば、他の成分を含むこ
とは、本発明の水ガラス用硬化剤製造用のリン酸
アルミニウムガラスとして、特に問題ないことで
ある。
このリン酸アルミニウムガラスを本発明の水ガ
ラス用硬化剤とするには、まず適当な粒度に粉砕
するのであるが、均一で耐水性ある硬化体を得る
ためには、一般的には細かい方が良いものの、実
用上88μm程度以下のものが適当である。
このリン酸アルミニウムガラス粉末は、縮合リ
ン酸アルミニウムと同様の耐水性を有する硬化体
が得られるのであるが、すでに述べたようにリン
酸アルミニウム粉末を、そのまま水ガラス用の硬
化剤として用いたのでは、粉末の粒度にもよる
が、可使時間が一般的には、30分程度以内、添加
量や粒度によつては瞬結に近くなつてしまうた
め、実用上は、可使時間を長くする必要がある。
そこでこれもすでに述べたように、上記リン酸ア
ルミニウムガラス粉末に対し、リン酸イオンと反
応して、リン酸アルミニウムガラス粉末粒子表面
に不溶性あるいは難溶性の塩を形成するような表
面化学処理剤0.01重量％以上にて表面化学処理し
たもの、例えば水酸化カルシウム0.01重量％以上
の懸濁液にて表面化学処理したものを水ガラス用
硬化剤とすると、硬化体の物性は、縮合リン酸ア
ルミニウムやリン酸アルミニウムガラスそのもの
とほとんど変わることなく、表面化学処理の程度
に応じて可使時間のみを容に長くすることが可能
になり、これをもつて本発明の硬化剤としたもの
である。
この不溶性あるいは難溶性の塩を形成する表面
処理剤としては、水酸化カルシウムの他にも水酸
化バリウム、水酸化ストロンチウム等があるが、
通常は安価な水酸化カルシウムで十分である。
またこの表面化学処理剤の量を0.01重量％以上
としたのは、0.01重量％以下では、その効果がほ
とんないためである。なおこの表面化学処理剤の
上限については、特に限定していないものの、処
理のための量を多くすればするほど、硬化時間の
長い硬化剤が得られるのであるが、通常は５重量
％以下で十分に硬化時間を長くすることが可能で
ある。
ところで上記リン酸アルミニウムガラス粉末の
表面化学処理により、可使時間が長くなる原因と
しては、例えば水酸化カルシウム添加懸濁水溶液
にて表面化学処理を行つたリン酸アルミニウムガ
ラス粒子表面を、顕微鏡にて観察すると、皮膜の
ような物質の生成が認められることから、これは
おそらくリン酸アルミニウムガラス粉末粒子の表
面近辺のP2O5と水酸化カルシウムからのCaイオ
ンとが反応し、粒子表面に不溶性の塩であるリン
酸カルシウムが生成しており、これが水ガラスと
の反応を妨げる層あるいは皮膜のような作用を有
しているためと考えられる。このリン酸アルミニ
ウムガラスの表面化学処理方法であるが、例えば
処理剤として、水酸化カルシウムを用いた場合、
リン酸アルミニウムガラスとの混合懸濁液は、最
初水酸化カルシウムにより、強アルカリ性を示す
が、反応が進み水酸化カルシウムが消費されるに
つれて、しだいにアルカリ性は弱くなつていき、
最終的にはほぼ中性を示すようになり、本発明に
おいては、この時点で表面化学処理を終了するよ
うにしている。従つて、表面化学処理するため添
加した水酸化カルシウムは、少量残存してもそれ
ほど問題ないのではとも考えられるが、本質的に
は処理終了後はすべて反応してしまい、硬化剤中
には少なくとも水酸化カルシウムとしては存在し
ないのである。
いずれにしてもこのような表面化学処理を行な
うことにより、硬化体の耐水性等には、何ら影響
を与えることなく可使時間を数時間以上、必要で
あれば１日以上にまで大幅に調整可能で、かつ良
好な水ガラス硬化剤が得られるのである。
本発明の硬化剤が有効な水ガラスとしては、特
に限定されず、通常市販されているケイ酸アルカ
リ溶液であれば全てに使用可能であり、また溶液
の形だけでなく、粉末状のケイ酸アルカリに水を
添加して混練使用するような場合にも勿論有効で
ある。また本発明にかゝる硬化剤の使用量は、水
ガラス100重量％に対し、20〜100重量％程度、３
号水ガラスの場合、通常30〜50重量％で特に高温
処理しなくとも耐水性の良好な硬化体が得られる
のである。
〔実施例〕
次に本発明の硬化剤について実施例によりさら
に詳しく説明する
実施例
ａ 硬化剤の製造方法
(1) リン酸アルミニウム（AlPO4）100ｇに対し、
リン酸二アンモニウム148ｇを混合した後、ア
ルミナルツボに入れ、アルミナのフタをした後
1450℃まで約１時間かけて昇温し、30分間保持
してから、水中に流し出し急冷しAl2O3約24重
量％P2O5約76重量％のリン酸アルミニウムガ
ラスを得た。次にこのリン酸アルミニウムガラ
スを乾燥後88μm以下に粉砕し、表面化学処理
リン酸アルミニウムガラス硬化剤製造用リン酸
アルミニウムガラス粉末（比較試料１）を得
た。
(2) (1)の方法にて得たリン酸アルミニウムガラス
粉末100ｇ％をビーカーに採取し、水酸化カル
シウム0.25ｇ、水100mlを加えてから、スター
ラにてかき混ぜながら同時にヒーターにて加熱
し、水分が蒸発するまで約１時間かけて加熱処
理し、水ガラス用の表面化学処理リン酸アルミ
ニウムガラス硬化剤（試料１）を得た。
(3) (1)の方法にて得たリン酸アルミニウムガラス
粉末100ｇに水酸化カルシウム0.5ｇ、水100ml
を加えたものをビーカーに入れ、以下(2)と同様
に処理して、表面化学処理リン酸アルミニウム
硬化剤（試料２）を得た。
(4) (1)の方法にて得たリン酸アルミニウムガラス
粉末100ｇに水酸化カルシウム0.75ｇ、水200ml
を加えたものをビーカーに入れ、水分が蒸発す
るまで約２時間かけて処理し、表面化学処理リ
ン酸アルミニウム硬化剤（試料３）を得た。
(5) (4)と同様の方法ただし水酸化カルシウム添加
量を1.0ｇとして処理し、表面化学処理リン酸
アルミニウム硬化剤（試料４）を得た。以上の
水酸化カルシウムによる表面化学処理において
は、すべて水が蒸発する前に、溶液はほぼ中性
を示すことを確認している。
(6) (1)の方法にて得たリン酸アルミニウムガラス
粉末100ｇをビーカーに採取し、水酸化カルシ
ウム2.5ｇ、水200mlを加えてから、湯浴上にて
約40℃に加熱しながらスターラにて溶液がほぼ
中性を示すまで約48時間かき混ぜた後、吸引口
過し固形分を採取してから乾燥し、水ガラス用
の表面化学処理リン酸アルミニウムガラス硬化
剤（試料５）を得た。
以上の今回の硬化剤の製造実施例においては、
処理時間を早めるため、高温にて処理している
が、処理時間さえ許されれば、より低温にて表面
化学処理した方が、より緻密な層あるいは皮膜が
生成するため、処理剤が同量であれば、可使時間
をより長くすることができることを確認してい
る。
ｂ 可使時間
水ガラスと前記製造方法で得られた各硬化剤を
混合したときの可使時間について、次のような検
討を行なつた。
市販の３号水ガラス（Na2O9.4重量％、
SiO229.4重量％）100重量％に対し、前述の各硬
化剤を夫々40重量％の割合にて混合したものを、
それぞれ約３分間混合した後、ポリスチロール製
の37mm〓×50mmＬ容器に半分程度入れて密閉し、
５〜20分間隔で時々容器をさかさまにしたとき、
流動性のなくなる時間をもつて可使時間とした。
結果は第１表のとおりである。なお本試験は約21
℃の室内にて行つた。
[Industrial Application Field] The present invention is directed to solutions of sodium silicate, potassium silicate, etc.
This relates to a hardening agent for so-called water glass. [Prior Art] Water glass is inexpensive, non-toxic, and has been widely used as a binder in adhesives, paints, and the like. However, when water glass is air-dried and cured as it is, the alkali silicate itself, which is a constituent of water glass, is water-soluble, resulting in a cured product with very poor water resistance. For this reason, various curing agents such as sodium silicate, aluminum phosphate, condensed aluminum phosphate, and acetate ester have been used to improve water resistance and adjust curing time, but they do not take long curing times. The reality is that there is still nothing that is satisfactory, such as poor water resistance. For example, soda silica, which is generally well known as a hardening agent for water glass, is a hazardous substance, subject to various regulations when used, has a short pot life, and the water resistance of the cured product is still not sufficient. It has the disadvantage of not being able to tell. In addition, condensed aluminum phosphate, which is said to have relatively good physical properties in terms of water resistance,
In manufacturing, the condensation process requires a special manufacturing method, which is quite complicated, making it difficult to obtain inexpensive products, and it has the drawbacks that it is also difficult to adjust the pot life. . In any case, each curing agent has its advantages and disadvantages, and the reality is that there is no one that can easily adjust pot life and has good water resistance. [Problems to be Solved by the Invention] Therefore, the present invention provides a water glass hardening agent whose cured product exhibits good water resistance when used as a hardening agent for water glass, and whose pot life can be easily adjusted. The purpose is to [Means for Solving the Problems] In order to achieve the above object, the present inventors have made various studies and found that aluminum phosphate glass has good water resistance similar to condensed aluminum phosphate as a hardening agent for water glass. We obtained the knowledge that this shows that However, aluminum phosphate glass as it is has the disadvantage of a short pot life, and when actually used as adhesives, paints, etc., products with a long pot life are often required. . As a result of further studies, we found that the surface of aluminum phosphate glass powder was chemically treated with a treatment agent that reacts with phosphate ions to form an insoluble or poorly soluble salt on the surface of the aluminum phosphate glass powder particles. For example, if a surface chemically treated with calcium hydroxide suspension is used as a hardening agent for water glass, the physical properties of the hardened product will be almost the same as condensed aluminum phosphate or aluminum phosphate glass itself, and the pot life will be shortened. It was found that it could be easily stretched, and was used as the curing agent of the present invention. By the way, aluminum phosphate glass essentially consists of alumina (Al 2 O 3 ) and phosphoric anhydride (P 2 O 5 ), and has continuous -O-Al-O-P-O- bonds. It is said that there are. In the production of aluminum phosphate glass used in the production of the curing agent of the present invention, alumina or aluminum hydroxide, etc. may be used as the Al 2 O 3 source.
Possible P 2 O 5 sources include phosphoric acid and ammonium salts of phosphoric acid, but other sources include Al 2 O 3 and P 2 O 5 , which are compounds of Al 2 O 3 and P 2 O 5 , and Al 2 O 3 . It can be produced by appropriately mixing and adjusting 3P 2 O 5 and the like, melting it at high temperature, and then rapidly cooling it. The vitrification range of the Al 2 O 3 −P 2 O 5 system is generally
Al 2 O 3 ・ 3P 2 O 5 and Al 2 O 3 ・
Al 2 O 3 30 slightly richer in Al 2 O 3 than the eutectic composition of P 2 O 5
It has been found that glasses with weight % P 2 O 5 of up to 70 weight % can be obtained. Although it is possible to obtain glass with a composition other than this, there are
As the amount of Al 2 O 3 increases, the amount of evaporation of P 2 O 5 increases, making it more difficult to manufacture aluminum phosphate glass. An aluminum phosphate glass within the above range is sufficient. It should be noted that the inclusion of other components is not permitted in the production of the hardening agent for water glass of the present invention, as long as they do not significantly change the essential properties of aluminum phosphate glass, such as solubility in water or alkaline aqueous solutions. This is not a particular problem for aluminum phosphate glass. In order to use this aluminum phosphate glass as the hardening agent for water glass of the present invention, it is first ground to an appropriate particle size, but in order to obtain a uniform and water-resistant hardened product, generally the finer the particle size the better. Although it is good, for practical purposes, a material with a diameter of about 88 μm or less is appropriate. This aluminum phosphate glass powder produces a cured product with water resistance similar to that of condensed aluminum phosphate, but as mentioned above, aluminum phosphate powder can be used as a hardening agent for water glass. Although it depends on the particle size of the powder, the pot life is generally within about 30 minutes, but depending on the amount added and the particle size, it can approach instant setting, so in practical terms, it is recommended to use a longer pot life. There is a need to.
Therefore, as already mentioned, the above aluminum phosphate glass powder is treated with a surface chemical treatment agent of 0.01 which reacts with phosphate ions to form an insoluble or poorly soluble salt on the surface of the aluminum phosphate glass powder particles. If a hardening agent for water glass is one whose surface has been chemically treated with a concentration of at least 0.01% by weight of calcium hydroxide, for example, the physical properties of the hardened product will be similar to that of condensed aluminum phosphate or Although it is almost the same as aluminum phosphate glass itself, it is possible to significantly lengthen the pot life depending on the degree of surface chemical treatment, and this makes it the curing agent of the present invention. Surface treatment agents that form this insoluble or poorly soluble salt include barium hydroxide, strontium hydroxide, etc. in addition to calcium hydroxide.
Usually, inexpensive calcium hydroxide is sufficient. The reason why the amount of the surface chemical treatment agent is set to 0.01% by weight or more is that if it is less than 0.01% by weight, the effect is almost negligible. The upper limit of this chemical surface treatment agent is not particularly limited, but the larger the amount for treatment, the longer the curing time will be obtained, but usually it is 5% by weight or less. It is possible to sufficiently lengthen the curing time. By the way, the reason why the surface chemical treatment of the aluminum phosphate glass powder increases the pot life is as follows. When observed, the formation of a film-like substance is observed, which is probably due to a reaction between P 2 O 5 near the surface of the aluminum phosphate glass powder particles and Ca ions from calcium hydroxide, resulting in the formation of insoluble substances on the particle surface. This is thought to be because calcium phosphate, a salt of water glass, is produced, and this acts like a layer or film that prevents the reaction with water glass. In this method of chemically treating the surface of aluminum phosphate glass, for example, when calcium hydroxide is used as the treatment agent,
The mixed suspension with aluminum phosphate glass initially exhibits strong alkalinity due to calcium hydroxide, but as the reaction progresses and calcium hydroxide is consumed, the alkalinity gradually becomes weaker.
Eventually, the surface becomes almost neutral, and in the present invention, the surface chemical treatment is completed at this point. Therefore, it is thought that calcium hydroxide added for surface chemical treatment may not cause much of a problem even if a small amount remains, but essentially all of the calcium hydroxide has reacted after the treatment is completed, and at least It does not exist as calcium hydroxide. In any case, by performing this kind of surface chemical treatment, the pot life can be significantly adjusted to several hours or more, or even one day or more if necessary, without affecting the water resistance etc. of the cured product. This makes it possible to obtain an excellent water glass hardening agent. The water glass for which the hardening agent of the present invention is effective is not particularly limited, and can be used in any alkaline silicate solution that is normally commercially available. Of course, it is also effective when water is added to an alkali and kneaded. Further, the amount of the curing agent used in the present invention is about 20 to 100% by weight, 3% by weight, based on 100% by weight of water glass.
In the case of No. 1 water glass, a cured product with good water resistance can be obtained at 30 to 50% by weight, even without special high-temperature treatment. [Example] Next, the curing agent of the present invention will be explained in more detail with reference to Examples. Example a Method for producing a curing agent (1) For 100 g of aluminum phosphate (AlPO 4 ),
After mixing 148g of diammonium phosphate, put it in an alumina pot and cover it with alumina.
The temperature was raised to 1450° C. over about 1 hour, held for 30 minutes, and then poured into water and rapidly cooled to obtain an aluminum phosphate glass containing about 24% by weight of Al 2 O 3 and about 76% by weight of P 2 O 5 . Next, this aluminum phosphate glass was dried and ground to 88 μm or less to obtain an aluminum phosphate glass powder (comparative sample 1) for producing a surface chemically treated aluminum phosphate glass hardening agent. (2) Collect 100g% of the aluminum phosphate glass powder obtained by the method in (1) into a beaker, add 0.25g of calcium hydroxide and 100ml of water, stir with a stirrer and heat with a heater at the same time. Heat treatment was performed for about 1 hour until the water evaporated, to obtain a surface chemically treated aluminum phosphate glass hardening agent for water glass (sample 1). (3) 100g of aluminum phosphate glass powder obtained by method (1), 0.5g of calcium hydroxide, and 100ml of water.
was added to a beaker and treated in the same manner as in (2) below to obtain a surface chemically treated aluminum phosphate curing agent (Sample 2). (4) 100g of aluminum phosphate glass powder obtained by method (1), 0.75g of calcium hydroxide, and 200ml of water.
The mixture was placed in a beaker and treated for about 2 hours until the water evaporated to obtain a surface chemically treated aluminum phosphate curing agent (sample 3). (5) Processed in the same manner as in (4) except that the amount of calcium hydroxide added was 1.0 g to obtain a surface chemically treated aluminum phosphate curing agent (Sample 4). In all of the above surface chemical treatments using calcium hydroxide, it has been confirmed that the solution becomes almost neutral before the water evaporates. (6) Collect 100g of the aluminum phosphate glass powder obtained by the method in (1) into a beaker, add 2.5g of calcium hydroxide and 200ml of water, and stir while heating it to about 40℃ on a hot water bath. After stirring for about 48 hours until the solution became almost neutral, the solid content was collected through a suction port and dried to obtain a surface chemically treated aluminum phosphate glass hardening agent for water glass (sample 5). Ta. In the production example of the curing agent described above,
In order to speed up the treatment time, the treatment is carried out at a high temperature, but if the treatment time is allowed, surface chemical treatment at a lower temperature will produce a denser layer or film, so even if the same amount of treatment agent is used, If so, we have confirmed that pot life can be extended even further. b. Pot life The following studies were conducted regarding the pot life when water glass and each curing agent obtained by the above manufacturing method were mixed. Commercially available No. 3 water glass (Na 2 O 9.4% by weight,
A mixture of each of the above-mentioned curing agents at a ratio of 40% by weight to 100% by weight (SiO 2 29.4% by weight),
After mixing each for about 3 minutes, pour about half of the mixture into a polystyrene 37mm × 50mmL container and seal it tightly.
When the container is turned upside down every 5 to 20 minutes,
The time it takes to lose fluidity is defined as the pot life.
The results are shown in Table 1. This exam is approximately 21
It was carried out indoors at ℃.
【表】
これらの結果から明らかなように、本発明の硬
化剤は、従来の硬化剤ではなかなか困難な可使時
間の調整をかなり容易に行なえるという特徴を有
するものである。
なお、上記本発明にかゝる試料を使用した硬化
体は、実施例５の例を除き、24時間後には硬化し
ており、それらを沸騰水中にて５時間煮沸試験を
行なつた場合でも、ケイフツ化ソーダを硬化剤と
したものと比較しても表面の侵食はほとんどな
く、耐水性も良好なことが確認された。
また試料５を用いたものでも、48時間後にも、
硬化しており同様の耐水性試験を行つても問題な
いことを確認している。
ｃ 水ガラスモルタル硬化体の強度
試料Ａ，Ｂ，Ｃは硬化剤として前記試料４を用
い、試料Ｄはケイフツ化ソーダを用いて第２表に
示すような配合の水ガラスモルタルを調整し、型
枠に入れ２×２×８cmの供試体を作製し強度測定
を行なつたものである。なおモルタルを調整する
場合の水量は、モルタル中の水分が25重量％とな
るよう不足分は水道水を添加して調整した。
これら水ガラスモルタルの強度試験結果は第３
表の通りであつた。
これらの実施例では、硬化剤として可使時間の
比較的長い試料４を使用して試験を行つたが、実
施例に示した他の硬化剤（試料１、試料２、試料
３および試料５）を用いても、３日後の強度発現
性には、それほど差のないという結果を得てい
る。また本実施例のように水ガラスモルタルとし
た場合の可使時間については、水ガラスモルタル
が作業するに十分な流動性を有する時間とした場
合、実施例の第１表に示したそれぞれの硬化剤の
可使時間に近い値を得た。[Table] As is clear from these results, the curing agent of the present invention has the characteristic that the pot life can be adjusted quite easily, which is difficult to do with conventional curing agents. It should be noted that, except for the example of Example 5, the cured products using the samples according to the present invention were cured after 24 hours, and even when they were subjected to a 5-hour boiling test in boiling water. It was confirmed that there was almost no surface erosion and that the water resistance was good compared to that using sodium silicate as a hardening agent. Also, even with sample 5, even after 48 hours,
It has been confirmed that it has hardened and there is no problem even if a similar water resistance test is performed. c Strength of cured water glass mortar Samples A, B, and C used sample 4 as a hardening agent, and sample D used sodium silicate to prepare water glass mortar with the composition shown in Table 2. A specimen measuring 2 x 2 x 8 cm was prepared by placing it in a frame and its strength was measured. When adjusting the mortar, the amount of water was adjusted by adding tap water to make up for the shortage so that the moisture content in the mortar was 25% by weight. The strength test results of these water glass mortars are the third
It was as shown in the table. In these Examples, tests were conducted using Sample 4, which has a relatively long pot life, as a curing agent, but other curing agents (Sample 1, Sample 2, Sample 3, and Sample 5) shown in the Examples were used. The results show that there is not much difference in strength development after 3 days even when using . In addition, regarding the pot life when water glass mortar is used as in this example, if the water glass mortar has sufficient fluidity to work, the respective curing times shown in Table 1 of the example are as follows. A value close to the pot life of the agent was obtained.
【表】【table】
本発明の硬化剤は、単に表面化学処理の条件を
変化させることで、簡単に水ガラスの硬化時間を
長くすることが可能で、また強度発現性も良好
で、耐水性の面でも、問題のない硬化体が得られ
るものである。
The curing agent of the present invention can easily lengthen the curing time of water glass by simply changing the surface chemical treatment conditions, has good strength development, and has no problem with water resistance. The result is a cured product that is free of oxidation.
Claims (1)
酸イオンと反応して、不溶性あるいは難溶性の塩
を形成するような表面化学処理剤0.01重量％以上
とを、水中にて混合懸濁接触反応せしめることに
より、該リン酸アルミニウムガラス粒子表面に、
水ガラスとの反応を抑制するような不溶性あるい
は難溶性の層を形成せしめた表面化学処理リン酸
アルミニウムガラス粉末より成る水ガラス用硬化
剤。1 By subjecting aluminum phosphate glass powder to a mixing suspension catalytic reaction in water with 0.01% by weight or more of a surface chemical treatment agent that reacts with phosphate ions to form an insoluble or poorly soluble salt. , on the surface of the aluminum phosphate glass particles,
A hardening agent for water glass made of chemically treated aluminum phosphate glass powder that forms an insoluble or poorly soluble layer that inhibits reaction with water glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17831883A JPS6071563A (en) | 1983-09-28 | 1983-09-28 | Curing agent for water glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17831883A JPS6071563A (en) | 1983-09-28 | 1983-09-28 | Curing agent for water glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6071563A JPS6071563A (en) | 1985-04-23 |
| JPH0341422B2 true JPH0341422B2 (en) | 1991-06-24 |
Family
ID=16046381
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17831883A Granted JPS6071563A (en) | 1983-09-28 | 1983-09-28 | Curing agent for water glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6071563A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5024326A (en) * | 1973-06-05 | 1975-03-15 | ||
| JPS559634A (en) * | 1978-07-07 | 1980-01-23 | Showa Denko Kk | Resin composition |
| JPS56145151A (en) * | 1980-04-10 | 1981-11-11 | Taihei Chem Ind | Alkali silicate curing agent |
-
1983
- 1983-09-28 JP JP17831883A patent/JPS6071563A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5024326A (en) * | 1973-06-05 | 1975-03-15 | ||
| JPS559634A (en) * | 1978-07-07 | 1980-01-23 | Showa Denko Kk | Resin composition |
| JPS56145151A (en) * | 1980-04-10 | 1981-11-11 | Taihei Chem Ind | Alkali silicate curing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6071563A (en) | 1985-04-23 |
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