JPH01249638A - Production of hardener for water glass - Google Patents

Abstract

PURPOSE:To increase a yield rate of metastable Al(PO3)3 having hardening function, by using aluminum oxide added with MgO and by specifying a heat- treating temp. in synthesis of condensed aluminum phosphate as hardener for water glass. CONSTITUTION:The homogeneous aluminum oxide mixture is dissolved in phosphoric acid by heating, so as to be Al2O3:MgO:P2O5=(1):(0.2):(3) (molar ratio), thereafter evaporated, concd. and dried up. The obtd. dried material is crushed, thereafter heat-treated at 200-400 deg.C to the constant weight and crushed to fine particle after cooling to obtain the hardener. Since the hardener scarcely contains cubic system Al(PO3)3 having no hardening ability, but consists of only the metastable Al(PO3)3, water glass is headened in a short time with the hardener.

Description

Translated fromJapanese

【発明の詳細な説明】［産業上の利用分野コこの発明は水ガラスの建築業界におｉ−する建４４の不
燃化あるいは難燃化、化学装置や暖熱装置に用いられる
水ガラス基材はパテの硬化剤、耐火耐熱塗料、鉱物性の
絶縁物質、含浸物質及び被覆物質用の結合剤として利用
されている。[Detailed Description of the Invention] [Industrial Application Fields] This invention is applied to the construction industry of water glass, making it non-combustible or flame retardant, and water glass base material used in chemical equipment and heating equipment. It is used as a hardener for putty, as a binder for fire-resistant and heat-resistant paints, mineral insulation materials, impregnating materials, and coating materials.

［従来の技術］水ガラスは安価な無機接着剤であるが、硬化に時間か掛
かり、耐水性か良好でないことの理由で、単味の使用に
は自すがら限度がある。上記の欠点を改良するために種
々の硬化剤の添加か行なわれており、不燃性無機硬化剤
として古くから、ケイ弗化ナトリウムが知られている。[Prior Art] Water glass is an inexpensive inorganic adhesive, but its use as a single adhesive is limited because it takes a long time to cure and its water resistance is poor. In order to improve the above-mentioned drawbacks, various hardening agents have been added, and sodium silicofluoride has been known as a nonflammable inorganic hardening agent for a long time.

また縮合リン酸アルミニウム（特願公告昭４４−８９７
７号）ホウ酸カルシウム（特公昭４９−１０８１３号）
第一リン酸の金属塩を基′Ａ副とするケイ弗化物（特公
昭４９−１６２５３ｊ＋）等が硬化剤として用いられて
いる。Also, condensed aluminum phosphate (patent application publication 1989-897)
No. 7) Calcium borate (Special Publication No. 49-10813)
A silicofluoride (Japanese Patent Publication No. 49-16253j+) having a metal salt of primary phosphoric acid as the base A is used as a curing agent.

し発明が解決しようとする課題］しかし上記従来の技術のうち、最も効果的な硬化剤は、
縮合リン酸アルミニウム（特公昭４４−８９７７号）で
あるか、そのＸ線回折図を第１図に示す。横軸は走査角
度２０を示し、単位は。[Problems to be Solved by the Invention] However, among the above conventional techniques, the most effective curing agent is
The X-ray diffraction pattern of condensed aluminum phosphate (Japanese Patent Publication No. 44-8977) is shown in FIG. The horizontal axis indicates the scanning angle 20, in units of .

である。縦軸ＧＪＸ線回折強度を表わす。図中１は等軸
晶系Ａｌ　（１’０３）　３の回折ピークを、２は準安
定相Ａ、Ｑ−（Ｐ（ｈ）３０回折ピークを示す。この物
質は等軸晶系へｇ（ＰＯ３）３と準安定相へｌ　（ＰＯ
３）　３との混合物であり、特公昭４４−８９７７号に
記されたように、「第１段階で恒量になるまで最高４０
０℃に、第２段階で再び恒量となるまで最高７５０℃に
加熱する」事を特徴としているが、第１段階の熱処理温
度を変化した場合の生成物のＸ線回折図を第２図に示す
。第２図は水酸化アルミニウムとリン酸のみで合成した
縮合リン酸アルミニウムのＸ線回折図である。加熱処理
温度４００℃以上の場合は等軸晶系へＭ　（ＰＯ３）　
３のみとなり、準安定相ＡＱ　（ｐｏ３）　３は消滅す
る。又加熱処理温度が２５０℃では、準安定相Ａｎ　（
ＰＯ３）　ｓは合成てきない。等軸晶・系ＡＵ　（ＰＯ
３）　３と準安定相人文（ＰＯ３）３との硬化作用の比
較のために、次きの実験を行なった。マイカ粉　３００
重量部、八１１（ＰＯ３）３７５重量部、水ガラス３０
０重量部、水６０重量部を混合して、その泥しようを型
に流しく厚さ１０ｍｍの円柱状）、放置し硬化作用を観
察した。It is. The vertical axis represents GJX-ray diffraction intensity. In the figure, 1 indicates the diffraction peak of the equiaxed crystal system Al (1'03) 3, and 2 indicates the metastable phase A, Q-(P(h) 30 diffraction peak. This material changes to the equiaxed crystal system g( PO3)3 and metastable phase l (PO
3) It is a mixture of
0℃ and then heated to a maximum of 750℃ in the second step until the weight becomes constant again.Figure 2 shows the X-ray diffraction diagram of the product when the heat treatment temperature in the first step is changed. show. FIG. 2 is an X-ray diffraction diagram of condensed aluminum phosphate synthesized using only aluminum hydroxide and phosphoric acid. If the heat treatment temperature is 400℃ or higher, it will change to equiaxed crystal system (PO3)
3, and the metastable phase AQ (po3) 3 disappears. Moreover, when the heat treatment temperature is 250°C, the metastable phase An (
PO3) s cannot be synthesized. Equiaxed system AU (PO
3) The following experiment was conducted to compare the hardening effects of 3) and metastable soujinbun (PO3) 3. Mica powder 300
Parts by weight, 811 (PO3) 375 parts by weight, 30 parts by weight of water glass
0 parts by weight and 60 parts by weight of water were mixed, and the slurry was poured into a mold (cylindrical shape with a thickness of 10 mm), left to stand, and the hardening effect was observed.

八ｌ　（ＰＯ３）　３としては、等軸晶系と準安定相を
用いた。準安定相を用いた物は２４時間以内に硬化した
か、等軸晶系の物は１週間経過しても硬化現象は認めら
れなかった。等軸晶系メタリン酸アルミニウムへｌ　（
１’０３）　３は硬化作用か全くなく、準安定相メタリ
ン酸アルミニウムＡ、Ｑ　（［’０３）　３が硬化作用
をもつことが分かった。従って加熱ＩＡ理効果により等
軸晶系Δｙ　（ＰＯ３）　３の生成を極力押さえ、準安
定相Δｘ　（ＰＯ３）　３の合成率を犬にすることを目
的としている。As 8l(PO3)3, an equiaxed crystal system and a metastable phase were used. The product using the metastable phase was cured within 24 hours, and the product using the equiaxed crystal system showed no hardening phenomenon even after one week had passed. To equiaxed aluminum metaphosphate (
It was found that 1'03) 3 had no hardening effect at all, and the metastable phase aluminum metaphosphates A and Q (['03)3 had a hardening effect. Therefore, the purpose is to suppress the formation of the equiaxed crystal system Δy (PO3) 3 as much as possible by the heating IA process effect, and to minimize the synthesis rate of the metastable phase Δx (PO3) 3.

［課題を解決するための手段］準安定相Ａ文（ＰＯ３）　３の合成率を大にするために
、種々の添加物の影響を調べた。添加物としては、Ｃａ
Ｏ，ＺｎＯ，ＭｇＯ，ＺｒＯ２，Ｙｚ［］３等を用いた
。[Means for solving the problem] In order to increase the synthesis rate of metastable phase A (PO3) 3, the effects of various additives were investigated. As an additive, Ca
O, ZnO, MgO, ZrO2, Yz[]3, etc. were used.

ＣａＯ，ＺｎＯ，ＺｒＯ２，Ｙ２Ｏ３等の添加の場合は
、第２図と同様で、加熱処理温度４００℃以上の場合は
等軸晶系ＡＵ　（ＰＯ３）　３のみて、準安定相人文（
ＰＯ３）　３をつるためには、４００℃以下で熱処理を
行なう必要がある。ＭｇＯ添加の場合は第３図に示す。In the case of addition of CaO, ZnO, ZrO2, Y2O3, etc., it is the same as shown in Fig. 2, and when the heat treatment temperature is 400°C or higher, the equiaxed crystal system AU (PO3) 3 becomes metastable.
In order to obtain PO3) 3, it is necessary to perform heat treatment at 400°C or lower. The case of MgO addition is shown in FIG.

加熱処理温度５５０℃でも準安定相Ａｐ　（ＰＯ３）　
３は安定に存在する。多少の等軸晶系ｕ　（ＰＯ３）　
３を伴っている。準安定相と等軸品系との量比を見るた
めに、加熱処理温度とＸ線回折強度比ＩＢ／■ｃ［準安
定相へｉ　（ＰＯ３）　３の面間隔５．４８人のピーク
の高さをＩＢ、等軸晶系Ａ父（ＰＯ３）３の面間隔４３
４人のピークの高さを■、とする］との関係を第４図に
示す。横軸は加熱処理温度（’Ｃ）を、縦軸はＩｎ／Ｉ
ｃを表わす。第４図に示したように１、／Ｉｏは４００
℃最大であるが、４００℃より少し上昇すると急激に減
少し、　５００℃で最低となり、　５００℃以上ではま
た増加するが、　７００℃が極大である。従って準安定
相ＡＪ！　（ＰＯ３）　３の合成率を大にするためには
、加熱処理温度４００℃以下に保つ必要がある。工業的
にはＭｇＯ添加、加熱処理温度は絶対に４００℃以下に
保つことである。ＭｇＯ以外の添加物又は不純物の影響
により準安定相へ、Ｑ　（ＰＯ３）　３の合成率が左右
されることがある。Metastable phase Ap (PO3) even at heat treatment temperature of 550℃
3 exists stably. Some equiaxed crystal system u (PO3)
It is accompanied by 3. In order to see the quantity ratio of the metastable phase and the equiaxed product system, we calculated the heat treatment temperature and the X-ray diffraction intensity ratio IB/■c [to the metastable phase i (PO3) 3 interplanar spacing 5.48 peak height. IB, equiaxed crystal system A father (PO3) 3 interplanar spacing 43
The peak height of the four people is assumed to be .] is shown in Fig. 4. The horizontal axis is the heat treatment temperature ('C), and the vertical axis is In/I.
represents c. As shown in Figure 4, 1, /Io is 400
The temperature is maximum at ℃, but it decreases rapidly when the temperature rises slightly above 400℃, reaches the minimum at 500℃, increases again above 500℃, and reaches its maximum at 700℃. Therefore, the metastable phase AJ! (PO3) In order to increase the synthesis rate of 3, it is necessary to maintain the heat treatment temperature at 400° C. or lower. Industrially, the MgO addition and heat treatment temperatures must be kept below 400°C. The synthesis rate of Q (PO3) 3 may be influenced by the influence of additives or impurities other than MgO into a metastable phase.

［作　　　用］上記のように、縮合リン酸アルミニウムには等軸晶系へ
交（ＰＯ３）３と準安定相Ａｆｌ（ＰＯ３）　３との両
者が存在し、硬化作用に有効なのは準安定相へｘ　（Ｐ
Ｏ３）　３であることが分かる。準安定相を合成するた
めには、ＭｇＯを添加した酸化アルミニウムが不可欠て
あり、しかも加熱処理温度は絶対に４００℃以下にすれ
は、純度９９％以上の準安定相へｌ　（ＰＯ３）　３を
高収率てうることができる。[Function] As mentioned above, condensed aluminum phosphate has both the equiaxed crystal system (PO3)3 and the metastable phase Afl(PO3)3, and it is the metastable phase that is effective for the hardening effect. x (P
It can be seen that O3) is 3. In order to synthesize a metastable phase, aluminum oxide doped with MgO is essential, and the heat treatment temperature must be below 400°C to convert l (PO3) 3 into a metastable phase with a purity of 99% or higher. It can be obtained in high yield.

［実　施　例］３２０ｇの水酸化アルミニウム（又は２１０ｇの酸化ア
ルミニウム）と１８〜３４ｇの酸化マグネシウムを均一
に混合した粉末を、１３００ｇのリン酸（８５％）中に
攪はんしながら加え、加熱溶解させた後、蒸発、濃縮を
行ない乾固させる。溶液の加熱温度は、溶液が沸騰しな
い様に、徐々に温度を上げながら行なう。乾固物は　１
１０℃で十分に乾燥した後、空気の流通をよくし、中ま
て反応させるため、粗粉砕し、　３８０℃で恒量になる
まて約３時間加熱し、放冷後細粉砕して硬化剤として用
いる。この際に得られた物質のＸ線回折図を第５図に示
す。準安定相へＭ　（ＰＯ３）　３のみで、等軸晶系へ
Ｕ（ＰＯ３）３はほとんど認められない。[Example] A uniformly mixed powder of 320 g of aluminum hydroxide (or 210 g of aluminum oxide) and 18 to 34 g of magnesium oxide was added to 1300 g of phosphoric acid (85%) with stirring, and heated. After dissolving, evaporate and concentrate to dryness. The heating temperature of the solution is carried out while gradually increasing the temperature so that the solution does not boil. The dry matter is 1
After sufficiently drying at 10°C, it is coarsely ground to improve air circulation and react inside, heated at 380°C for about 3 hours until it reaches a constant weight, left to cool, and then finely ground to remove the curing agent. used as The X-ray diffraction pattern of the substance obtained at this time is shown in FIG. Only M(PO3)3 enters the metastable phase, and almost no U(PO3)3 enters the equiaxed crystal system.

［発明の効果］この発明は、以上説明したように、簡単に、安価に作る
ことができ、硬化作用も非常に良好である。次ぎにレジ
ライ［・−水ガラス系についての硬化作用を第６図に示
す。レジライトは無定形シリカと準安定相メタリン酸ア
ルミニウムへ’ｌ　（ＰＯ３）　３の１：１　（重量比
）の物である。横軸はレジライ）・の重量％を、縦軸は
硬化時間（単位は日）を示す。レジライト２０％、水ガ
ラス濃度３０％が一番効果がある。[Effects of the Invention] As explained above, the present invention can be manufactured easily and inexpensively, and has a very good curing effect. Next, FIG. 6 shows the hardening effect of Regirai [.--water glass system. Resilite is a 1:1 (weight ratio) of amorphous silica and metastable phase aluminum metaphosphate. The horizontal axis shows the weight percent of Regirai), and the vertical axis shows the curing time (in days). A concentration of 20% Regilight and 30% water glass is most effective.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図は特公昭４４−８９７７号の縮合リン酸アルミニ
ウムのＸ線回折図を示すもので、横軸（Ｊ走査角度２θ
を示し、単位は°である。縦軸はＸ線回折強度を表わす
。図中１は等軸晶系Ａｊ−（ＰＯ３）ｓの回折ピークを
、２は準安定相Δｌ　（ＰＯ３）　３の回折ピークを示
す。対陰極はＣｕである。第２図は水酸化アルミニウムとリン酸のみて合成した縮
合リン酸アルミニウムの加熱処理温度の相違によるＸ線
回折図を示す。横軸は走査角度２０を示し、単位ＧＪ°
である。縦軸はＸ線回折強度を表わす。図中■は２５０
℃、ＩＩは３５０℃、ＩＩＩは４００℃、ＩＶは５５０
℃加熱処理物を表わし、１は等軸晶系ｘＪ−（ＰＯ３）
３の回折ピークを、２は準安定相へｘ　（ＰＯ３）　３
の回折ピークを示す。対陰極はＣｕである。第３図は酸化マグネシウム添加の場合の加熱処理温度の
相違によるＸ線回折図を示す。横軸は走査角度２０を示
し、単位は°である。縦軸はＸ線回折強度を表わす。図
中、■は２５０℃、ＩＩは４００℃、Ｉｌｌは５５０℃
加熱処理物を表わし、１は等軸孔系ｕ（ｐｏａＬの回折
ピークを、２は準安定相Ａ９．（ＰＯ３）３の回折ピー
クを示す。対陰極はＣｕである。第４図は第３図と同じ組成物で、等軸晶系と準安定相の
Ｘ線回折強度比Ｉ　ｌ］／　Ｉ　ｃと加熱処理温度の関
係を示す。横軸は加熱処理温度、単位は°である。縦軸
はＸ線回折強度比ＩＢ／Ｔｃを示す。第５図は本発明の準安定相メタリン酸アルミニウムＡρ
（ＰＯ３）３のＸ線回折図である。横軸は走査角度２０
を示し、単位は°である。縦軸はＸ線回折強度を表わす
。図中２は準安定相Δｌ　（ＰＯ３）　３の回折ピーク
を示す。対陰極はＣｕである。第６図はレジライｉ・−水ガラス系にっての硬化作用を
示す。レジライトは無定形シリカと準安定相メタリン酸
アルミニウムの１：１　（重量比）混合物であり、横軸
は準安定相メタリン酸アルミニウムの重量％を、縦軸は
硬化時間（単位口）を示す。Figure 1 shows the X-ray diffraction diagram of condensed aluminum phosphate published in Japanese Patent Publication No. 44-8977.
The unit is °. The vertical axis represents the X-ray diffraction intensity. In the figure, 1 indicates the diffraction peak of the equiaxed crystal system Aj-(PO3)s, and 2 indicates the diffraction peak of the metastable phase Δl(PO3)3. The anticathode is Cu. FIG. 2 shows X-ray diffraction patterns of condensed aluminum phosphate synthesized using only aluminum hydroxide and phosphoric acid at different heat treatment temperatures. The horizontal axis shows the scanning angle 20, unit GJ°
It is. The vertical axis represents the X-ray diffraction intensity. ■ in the diagram is 250
℃, II is 350℃, III is 400℃, IV is 550℃
℃ heat treated product, 1 is equiaxed crystal system xJ-(PO3)
The diffraction peak of 3 is transferred to the metastable phase of 2x (PO3) 3
shows the diffraction peak of The anticathode is Cu. FIG. 3 shows X-ray diffraction patterns depending on the heat treatment temperature when magnesium oxide is added. The horizontal axis indicates the scanning angle 20, in degrees. The vertical axis represents the X-ray diffraction intensity. In the figure, ■ is 250℃, II is 400℃, and Ill is 550℃
1 represents the diffraction peak of the equiaxed pore system u(poaL), and 2 represents the diffraction peak of the metastable phase A9.(PO3)3. The anticathode is Cu. The relationship between the X-ray diffraction intensity ratio I l / I c of the equiaxed crystal system and the metastable phase and the heat treatment temperature is shown for the same composition as in the figure. The horizontal axis is the heat treatment temperature, and the unit is °. The vertical axis is the heat treatment temperature. The axis shows the X-ray diffraction intensity ratio IB/Tc. Figure 5 shows the metastable phase aluminum metaphosphate Aρ of the present invention.
It is an X-ray diffraction diagram of (PO3)3. The horizontal axis is the scanning angle 20
The unit is °. The vertical axis represents the X-ray diffraction intensity. In the figure, 2 indicates the diffraction peak of the metastable phase Δl (PO3) 3. The anticathode is Cu. FIG. 6 shows the hardening effect of the Regirai i-water glass system. Resilite is a 1:1 (weight ratio) mixture of amorphous silica and metastable aluminum metaphosphate, where the horizontal axis shows the weight percent of the metastable aluminum metaphosphate, and the vertical axis shows the curing time (unit unit). .

Claims (1)

Translated fromJapanese

【特許請求の範囲】[Claims]１　水ガラス用硬化剤としてＡｌ＿２Ｏ＿３：ＭｇＯ：
Ｐ＿２Ｏ＿５＝１：０．２：３（モル比）となるように
、酸化アルミニウム均一混合物をリン酸に加熱溶解した
後、蒸発、濃縮、乾固させ、乾固物を粉砕した後、恒量
になるまで２００〜４００℃に熱処理して、準安定相の
メタリン酸アルミニウムを得ることを特徴とする水ガラ
ス用硬化物の製造方法。1 Al_2O_3:MgO as a hardening agent for water glass:
After heating and dissolving a homogeneous aluminum oxide mixture in phosphoric acid so that P_2O_5 = 1:0.2:3 (molar ratio), it is evaporated, concentrated, and dried, and the dry matter is pulverized to a constant weight. 1. A method for producing a cured product for water glass, comprising heat-treating at 200 to 400° C. to obtain aluminum metaphosphate in a metastable phase.