JP5425326B2 - Molded body for heat insulating material and manufacturing method thereof - Google Patents

Description

  The present invention relates to a composition for a heat insulating material, a molded body for a heat insulating material, and a production method thereof.

  As one of the inorganic heat insulating materials, heat insulation of compact type or amorphous composition type using crystalline calcium silicate (including hydrate) such as zonotlite, tobermorite, gyrolite, wollastonite The material is known. Among them, in particular, a heat insulating material using at least one crystalline calcium silicate hydrate of zonotlite and tobermorite as a raw material is excellent in heat resistance, heat insulating property, mechanical strength, etc., and is widely used industrially. Yes.

  In order to further improve the heat insulating properties of the heat insulating material using the crystalline calcium silicate hydrate, various attempts have been made conventionally. For example, an attempt to carbonate crystalline calcium silicate hydrate to convert it to amorphous silica and calcium carbonate (Patent Document 1), followed by further acid treatment with hydrochloric acid after carbonation to convert the calcium carbonate into a water-soluble calcium salt. Instead, an attempt is made to wash with water and remove calcium salt to make only amorphous silica (Patent Document 2).

  These attempts improve thermal insulation by converting crystalline calcium silicate hydrate to amorphous silica to increase micropores. However, these have problems that the molded body is easily deformed by the shrinkage of the amorphous silica during drying after molding, and it is difficult to stably obtain a desired molded body. Furthermore, regarding what is acid-treated and washed with water, there is also a problem of drainage of a water-soluble calcium salt. In addition, a pressure vessel is required to efficiently perform carbonation. In the case of Patent Document 2, an extra step of acid treatment and water washing is required in addition to the pressure vessel, both of which are expensive equipment and / or Alternatively, a complicated process is required, leading to an increase in manufacturing cost.

  As an attempt for further improvement, an attempt is made to add an alkali silicate to crystalline calcium silicate hydrate, then carbonate, and further perform acid treatment with hydrochloric acid or the like (Patent Document 3).

  This attempt is based on the fact that granular amorphous silica derived from alkali silicate adheres to amorphous silica in which crystalline calcium silicate hydrate is converted by carbonation. Although the crystalline silica is reinforced to improve the shrinkage during drying, the problem of water-soluble calcium salt drainage and the problem of increased production costs remain as described above.

  In addition, attempts have been made to treat crystalline calcium silicate hydrate with an organic acid (Patent Document 4). However, using an expensive organic acid leads to an increase in production cost and an improvement in heat insulation. The effect is not enough.

  Therefore, it is a composition for thermal insulation that uses crystalline calcium silicate (including hydrates) such as zonotlite, tobermorite, gyrolite, and wollastonite as a raw material. Moreover, development of a practical composition for a heat insulating material obtained by a production method free from the problem of drainage of calcium salt is desired.

Japanese Patent Publication No. 60-35318 Japanese Examined Patent Publication No. 61-58436 Japanese Patent Publication No. 6-102533 Japanese Patent Publication No. 5-13090

  The present invention is a composition for a heat insulating material using crystalline calcium silicate (including hydrates; hereinafter the same unless otherwise specified) such as zonotlite, tobermorite, gyrolite, wollastonite, etc. as a raw material. Thus, an object of the present invention is to provide a practical composition for a heat insulating material, which has a heat insulating property superior to that of a conventional product, and is obtained by a production method which is simple and free from calcium salt drainage. Another object of the present invention is to provide a heat insulating material molded body obtained by dehydrating and drying the heat insulating material composition.

  As a result of intensive studies to achieve the above object, the present inventors have found that a composition for a heat insulating material obtained by a specific production method can achieve the above object, and have completed the present invention.

That is, the present invention, the cross-sectional heated material compacts below and a manufacturing method.
1.1) at least one crystalline calcium silicate selected from the group consisting of zonotlite, tobermorite, gyrolite and wollastonite, and 2) calcium hydroxide, calcium carbonate, cement, amorphous calcium silicate hydrate , talc and at least one inorganic material selected from the group consisting of magnesium hydroxide, the obtained by reacting the phosphoric acid that the cross-sectional thermal material composition in the presence of water, for a thermal insulator formed body the density can be obtained by dehydrating formation and drying so that 0.1 to 0.3 g / cm ^3, a density of 0.1 to 0.3 g / cm ³ for a thermal insulator formed body.
2. The said composition for heat insulating materials is for heat insulating materials of the said claim | item 1 containing the composition A containing the at least 1 sort (s) of phosphoric acid calcium salt and phosphoric acid magnesium salt, and an amorphous silica. Molded body .
3. In the above item 1, the composition for a heat insulating material includes the composition B obtained by adding at least one crystalline calcium silicate selected from the group consisting of zonotlite, tobermorite, gyrolite, and wollastonite to the composition A. The molded object for heat insulating materials as described.
4). The composition for a heat insulating material contains at least one inorganic substance selected from the group consisting of calcium hydroxide, calcium carbonate, cement, amorphous calcium silicate hydrate, talc and magnesium hydroxide in the composition A. Item 2. The molded body for heat insulating material according to Item 1, comprising the added composition C.
5. The composition for a heat insulating material includes at least one crystalline calcium silicate selected from the group consisting of zonotlite, tobermorite, gyrolite and wollastonite in the composition A, and calcium hydroxide, calcium carbonate, cement, Item 2. The molded article for heat insulating material according to Item 1, comprising a composition D to which at least one inorganic substance selected from the group consisting of amorphous calcium silicate hydrate, talc and magnesium hydroxide is added.
6). The said crystalline calcium silicate is the molded object for heat insulating materials in any one of said claim | item 1-5 which is a secondary particle of the crystalline calcium silicate hydrate containing at least 1 sort (s) of a zonotolite and a tobermorite.
7). Item 7. The molded body for heat insulating material according to any one of Items 1 to 6, wherein the inorganic substance is calcium hydroxide.
8). Item 7. The molded article for heat insulating material according to any one of Items 1 to 6, wherein the inorganic substance is calcium hydroxide and cement.
9.1) At least one crystalline calcium silicate selected from the group consisting of zonotlite, tobermorite, gyrolite and wollastonite, and 2) calcium hydroxide, calcium carbonate, cement, amorphous calcium silicate hydrate , talc and at least one inorganic material selected from the group consisting of magnesium hydroxide, after obtaining by Ridan thermal material composition to be reacted with phosphoric acid in the presence of water, the heat insulating material The composition for heat insulation is dehydrated and dried so that the density of the molded body for heat insulation becomes 0.1 to 0.3 g / cm ^3, and the density is 0.1 to 0.3 g / cm ³ . Manufacturing method of a molded object .
10. Item 10. The method according to Item 9 , wherein the crystalline calcium silicate is a secondary particle of crystalline calcium silicate hydrate containing at least one of zonotolite and tobermorite.
11. Item 11. The method according to Item 9 or 10 , wherein the inorganic substance is calcium hydroxide.
12 Item 11. The method according to Item 9 or 10 , wherein the inorganic substance is calcium hydroxide and cement.
13. Any of the above items 9 to 12 , wherein a mixture containing the crystalline calcium silicate, the inorganic substance, and water is prepared, and phosphoric acid is added thereto while stirring the mixture , thereby obtaining the heat insulating material composition. The manufacturing method of crab.
14 Phosphoric acid was added to the mixture A obtained by adding phosphoric acid while stirring the mixture containing the crystalline calcium silicate and water, and the mixture containing the inorganic substance and water was stirred. Item 13. The production method according to any one of Items 9 to 12 , wherein the obtained mixture B is prepared, and the mixture A and the mixture B are further mixed to obtain the heat insulating material composition .

  Hereinafter, the composition for heat insulating material, the molded body for heat insulating material, and the production method of the present invention will be described.

Composition for heat insulating material and molded article for heat insulating material The composition for heat insulating material of the present invention includes: 1) at least one crystalline calcium silicate selected from the group consisting of zonotlite, tobermorite, gyrolite and wollastonite; 2) at least one inorganic substance selected from the group consisting of calcium hydroxide, calcium carbonate, cement, amorphous calcium silicate hydrate (CSH), talc, and magnesium hydroxide in the presence of water It is obtained by reacting with an acid.

  The composition for a heat insulating material of the present invention having the above characteristics is obtained by reacting a specific crystalline calcium silicate and an inorganic substance with phosphoric acid in the presence of water, and is made from a conventional crystalline calcium silicate as a raw material. The heat insulating property is improved as compared with the composition for a heat insulating material used as (reaction raw material), and it is obtained by a production method which is simple and does not have a problem of calcium salt drainage. The composition for a heat insulating material of the present invention and the molded body for a heat insulating material obtained by molding the composition are useful as a practical heat insulating material having improved heat insulating properties.

When a specific crystalline calcium silicate and an inorganic substance react with phosphoric acid in an equivalent amount in the presence of water, the composition for a heat insulating material of the present invention is converted from crystalline calcium silicate to a calcium salt of hydroxy (hydroxyl). Apatite (Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ ), vitrokite (Ca ₃ (PO ₄ ) ₂ ), etc.) and amorphous silica are formed, and calcium phosphate (monetite (CaPO ₃ (CaPO ₃ ( OH)), brushite (CaPO ₃ (OH) · 2H ₂ O), hydroxyapatite, vitrokite, etc.) and a magnesium salt of phosphoric acid (magnesium hydrogen phosphate, magnesium phosphate, etc.). The product after the reaction can be confirmed by powder X-ray diffraction analysis.

  That is, the basic composition of the composition for a heat insulating material of the present invention (equivalent reaction product with phosphoric acid) is composed of at least one phosphate of a calcium salt of phosphoric acid and a magnesium salt of phosphoric acid and amorphous silica. (The details will be described later, but the addition of an auxiliary material is allowed).

  However, when making it react by other than an equivalent, the composition for heat insulating materials of this invention can also take the case where the composition B-D illustrated below is included. In addition, since the detail of each composition is the content depending on manufacturing conditions (reaction conditions), it mentions later by the item of a manufacturing method.

  The composition B is a composition obtained by adding at least one crystalline calcium silicate selected from the group consisting of zonotlite, tobermorite, gyrolite and wollastonite to the composition A. That is, the raw material is a composition in which all of the inorganic substances react and a part of the crystalline calcium silicate remains unreacted.

  Composition C is a composition obtained by adding at least one inorganic substance selected from the group consisting of calcium hydroxide, calcium carbonate, cement, amorphous calcium silicate hydrate, talc and magnesium hydroxide to composition A. . That is, in the raw material, the crystalline calcium silicate has reacted, and a part of the inorganic substance remains unreacted.

  Composition D is composition A with at least one crystalline calcium silicate selected from the group consisting of zonotlite, tobermorite, gyrolite and wollastonite, and calcium hydroxide, calcium carbonate, cement, amorphous calcium silicate It is a composition to which at least one inorganic substance selected from the group consisting of hydrate, talc and magnesium hydroxide is added. That is, in the raw material, both the crystalline calcium silicate and the inorganic substance are partially unreacted.

  The composition for heat insulating material may be comprised only in either of composition AD, and may contain a well-known auxiliary material (additive) as needed. Although content of an auxiliary material is not limited, what is necessary is just to adjust according to the objective and a use in the range from which content of composition AD in the composition for heat insulating materials becomes 50 to 100 weight%.

  The type of the auxiliary material is not limited. For example, infrared shielding materials such as metal oxide, metal carbide (eg, silicon carbide), metal nitride (eg, silicon nitride), pigment, dye, fiber (organic fiber, Inorganic fibers, carbon fibers), polymers (resins), water repellents, existing fillers such as diatomaceous earth and bentonite, cement (non-reactive with phosphoric acid), aluminum lactate, aluminum sulfate, Aerosil from Evonik Dexa Name) and Cabot Nanogel (trade name), water-repellent fine silica, surfactants, flocculants, dispersants, coagulants, antifoaming agents, and the like.

  The auxiliary material may be added at any time in the production process as long as the effects of the present invention are not impaired. For example, during the synthesis of crystalline calcium silicate, before the reaction with phosphoric acid, after the reaction with phosphoric acid. Etc. can be added at any time. In addition, when the auxiliary raw material is added during the synthesis of crystalline calcium silicate or during the reaction with phosphoric acid, the auxiliary raw material itself may be involved in the reaction. From the viewpoint of sufficiently obtaining the action expected for the raw material, the auxiliary raw material is preferably added after the reaction with phosphoric acid.

  Although it is different from the auxiliary material, the crystalline calcium silicate is allowed to contain a small amount of other crystalline calcium silicate in addition to zonotlite, tobermorite, gyrolite and wollastonite as long as it does not affect the heat insulation. Is done. In this regard, in the present invention, if the total amount of zonotlite, tobermorite, gyrolite and wollastonite contains 80% by weight or more of crystalline calcium silicate, “zonotrite, tobermorite, gyro” It is treated as “at least one crystalline calcium silicate selected from the group consisting of wright and wollastonite”.

  In the present invention, the crystalline calcium silicate is preferably at least one of zonotlite and tobermorite, and more preferably secondary particles of crystalline calcium silicate hydrate containing at least one of zonotrite and tobermorite.

  In the present invention, it is preferable to use “calcium hydroxide” or “combination of calcium hydroxide and cement” as the inorganic substance. By using calcium hydroxide, heat insulation performance and the like are improved, and by using cement, drying shrinkage and the like can be reduced.

  The composition for a heat insulating material of the present invention can be used as a molded body for a heat insulating material by dehydrating and drying. Dehydration molding and drying conditions will be described later in the item of production method.

The density of the composition for heat insulating material and the molded body for heat insulating material is not limited, but is 0.05 g / cm ³ or more, preferably 0.1 to 1.2 g / cm ³ , more preferably 0.1 to 0. 6 g / cm ^3, more preferably from 0.1 to 0.3 g / cm ³ order. What is necessary is just to set this density suitably according to the objective and a use.

  Thermal insulation compositions can be used in applications where irregular-type thermal insulation materials are used. For example, joint materials, putty materials, and spraying materials that require thermal insulation (thermal insulation) and heat resistance (fire resistance) It can also be applied to insulation materials for heat insulating materials, kneaded heat insulation materials for devices with complicated shapes and piping.

  The molded body for thermal insulation can be used in applications where molded body type thermal insulation is used, and the size and shape are not limited. The size, shape, workability, handleability, and requirements of the object to be constructed Can be set as appropriate in consideration of the heat insulation performance, productivity and the like. Specifically, the thickness of a single plate in the case of a plate-like molded body for heat insulating material is usually preferably about several mm to 100 mm.

  Moreover, since the heat insulating material composition and the molded body for heat insulating material of the present invention also have humidity control properties, they can be used for humidity control building materials (including coating materials), as well as non-combustible building materials.

Composition for heat insulating material and method for producing molded article for heat insulating material The method for producing the composition for heat insulating material of the present invention is 1) at least one selected from the group consisting of zonotlite, tobermorite, gyrolite and wollastonite. The presence of water of crystalline calcium silicate and 2) at least one inorganic substance selected from the group consisting of calcium hydroxide, calcium carbonate, cement, amorphous calcium silicate hydrate, talc and magnesium hydroxide It is characterized by reacting with phosphoric acid below.

  As the at least one crystalline calcium silicate selected from the group consisting of zonotlite, tobermorite, gyrolite and wollastonite, any of those having no crystal water and hydrates having crystal water can be used. Further, existing crystals such as crystalline calcium silicate crystals (primary particles) and aggregates (secondary particles) thereof can be used.

  For example, secondary particles (aggregates) of crystalline calcium silicate hydrate mainly composed of zonotlite as disclosed in JP-B No. 54-1727 or an aqueous slurry thereof, Tobermorite as disclosed in JP-A No. 58-185432, etc. Crystalline calcium silicate hydrate secondary particles (aggregates) or aqueous slurries thereof, crystalline calcium silicate hydrate mainly containing gyrolite as disclosed in JP-B-60-29643 Secondary particles (aggregates), wollastonite obtained by heating secondary particles (aggregates) mainly composed of the above-mentioned zonotlite and tobermorite as described in JP-B-50-29493, etc. The secondary particles (aggregates) of crystalline calcium silicate can be preferably used.

  That is, the crystalline calcium silicate is preferably secondary particles from the viewpoints of moldability and physical properties. In addition, since calcium silicate hydrate or phosphoric acid is added with stirring calcium silicate in the presence of water so that the reaction between crystalline calcium silicate and phosphoric acid is uniformly performed, calcium silicate hydrate Or as calcium silicate, what is aqueous slurry form from the beginning as mentioned above can be utilized preferably.

  In particular, secondary particles of crystalline calcium silicate hydrate containing at least one of zonotolite and tobermorite can be preferably used in view of performance such as heat insulation and moldability.

Specifically, for example, in the case of secondary particles of zonotlite, a raw material slurry containing a calcareous raw material, a siliceous raw material, and water, adjusted so that the molar ratio of CaO / SiO _{2 in} the raw material is about 1.0. Is hydrothermally reacted with stirring to obtain an aqueous slurry composed of secondary particles of zonotlite. Although it does not limit as a calcareous raw material, For example, quick lime (calcium oxide), slaked lime (calcium hydroxide), carbide lees, calcium chloride, etc. can be used.

  Moreover, as a silicic acid raw material, one or more types, such as silica stone, silica sand, silica gel, white carbon, diatomaceous earth, ferrosilicon dust, shirasu, rice husk ash, can be used together.

  Further, the water content is usually 5 times or more (preferably 10 to 70 times by weight) the total amount of the calcareous material and the siliceous material.

In the case of secondary particles of tobermorite, the molar ratio of CaO / SiO _{2 in} the raw material may be adjusted to about 0.8 in the above.

  The conditions of the hydrothermal reaction of the raw material slurry are not limited as long as secondary particles of crystalline calcium silicate hydrate such as zonotlite and tobermorite are generated. For example, pressurization and heating in an autoclave while stirring the raw material slurry. do it.

Regarding the temperature and pressure during the hydrothermal reaction, the pressure is preferably about 8 to 50 kgf / cm ² , and the temperature is preferably about 170 to 260 ° C.

The molar ratio (CaO / SiO ₂ ), which is the mixing ratio of CaO in the calcareous raw material and SiO ₂ in the siliceous raw material, is around 1.0 (about 0.9 to 1.2) for zonotlite, and is 0.0 for tobermorite. Around 8 (about 0.7 to 0.9) is preferable.

  Moreover, the particle diameter of the secondary particles of crystalline calcium silicate hydrate such as zonotlite and tobermorite obtained by hydrothermal reaction is not limited, but is about 5 to 150 μm, and the primary particles constituting the secondary particles The length is about 1 to 20 μm. These particle sizes are values measured by microscopic observation.

  As the at least one inorganic substance selected from the group consisting of calcium hydroxide, calcium carbonate, cement, amorphous calcium silicate hydrate, talc and magnesium hydroxide, existing substances can be used. Regarding talc and magnesium hydroxide, commercially available chemicals, industrial chemicals, industrial products, industrial raw materials, and the like can be used.

  As the amorphous calcium silicate hydrate (CSH), CSH disclosed in Japanese Patent Publication No. 58-30259 can be used.

  Regarding calcium hydroxide, commercially available chemicals, industrial chemicals, industrial products, etc. can be used, as well as lime milk (calcium hydroxide suspension) obtained by dehydrating quick lime with water or hot water, and its lime milk It is possible to use a material that has been refined by processing with a homomixer or the like. Among inorganic substances, calcium hydroxide can be preferably used from the viewpoint of performance such as heat insulation, and a combination of calcium hydroxide and cement can also be preferably used.

  Regarding calcium carbonate, any crystal system of calcite, vaterite and aragonite can be used, and commercially available chemicals, industrial chemicals, industrial products, and the like can be used.

  As the cement, known cements such as Portland cement, alumina cement, blast furnace cement, fly ash cement, and mixed cement can be used.

  The conditions for reacting the crystalline calcium silicate and the inorganic substance with phosphoric acid in the presence of water may be appropriately set within a range not impairing the effects of the present invention, but under stirring for uniform reaction. A method of adding phosphoric acid to is preferable.

  There are no particular restrictions on the contact temperature for reaction with phosphoric acid, the addition rate of phosphoric acid, the concentration of phosphoric acid, etc., and these may be set as appropriate. For example, the contact temperature may be either room temperature or warming, and phosphoric acid can be press-fitted and brought into contact while being heated to about 200 ° C. using an autoclave. Moreover, the addition rate of phosphoric acid may be added slowly or rapidly. Phosphoric acid can be used either as a stock solution or a diluted solution, and an aqueous solution having a phosphoric acid concentration of 5 to 50% by weight is particularly preferable. As phosphoric acid, existing chemicals such as commercially available chemicals and industrial chemicals can be used.

  Moreover, about the reaction rate which makes crystalline calcium silicate and an inorganic substance react with phosphoric acid in presence of water, all may be made to react with phosphoric acid, and part may be made to react with phosphoric acid. Good. In the case of calcium silicate hydrate or calcium silicate, for example, 10 to 100% by weight can be reacted with phosphoric acid, and about 60% by weight or more is preferable in consideration of heat insulation performance.

  It is preferable that the inorganic substance reacts with phosphoric acid as a whole. However, an inorganic substance that does not react may be left as long as the effects of the present invention are not impaired. Moreover, you may refine | miniaturize the said inorganic substance using a homomixer etc. before making it react with phosphoric acid so that it may react easily with phosphoric acid.

  When all of the crystalline calcium silicate is reacted with phosphoric acid, a calcium salt of phosphoric acid such as hydroxyapatite and vitrokite and amorphous silica become a product. When a part is reacted, unreacted crystalline calcium silicate remains in the product.

  When the entire inorganic substance is reacted with phosphoric acid, a phosphate composed of at least one of a calcium salt of phosphoric acid and a magnesium salt of phosphoric acid becomes a product. When a part is reacted, an unreacted inorganic substance remains in the product. For example, when the inorganic substance is calcium hydroxide, a calcium salt of phosphoric acid such as monetite, hydroxyapatite, vitrokite becomes a product by reacting with phosphoric acid.

In addition, about the specific mixture ratio of crystalline calcium silicate, an inorganic substance, and phosphoric acid, it can determine by defining the following (i)-(iii), and after defining (i) first, (ii) and (iii ) In order.
(I) “Determine the blending ratio of crystalline calcium silicate and inorganic substance”
The blending ratio of the crystalline calcium silicate and the inorganic substance may be appropriately set within a range not impairing the effects of the present invention, but the molar amount of Ca or Mg in the inorganic substance relative to the molar amount of Ca in the crystalline calcium silicate. It is preferable to blend so that the value of the ratio (atomic ratio) is about 0.01 to 3. For example, when the crystalline calcium silicate is zonotlite and the inorganic substance is calcium hydroxide, the value of the ratio (atomic ratio) of the molar amount of Ca in calcium hydroxide to the molar amount of Ca in zonotlite is 0. The thing of the range of about 08-1.35 is preferable. When the crystalline calcium silicate is tobermorite and the inorganic substance is calcium hydroxide, the ratio (atomic ratio) of the molar amount of Ca in calcium hydroxide to the molar amount of Ca in tobermorite is 0. The thing of the range of about 1-1.6 is preferable.
(Ii) “Determine the blending ratio of crystalline calcium silicate and phosphoric acid”
The blending ratio of the crystalline calcium silicate and the phosphoric acid reacted with the crystalline calcium silicate may be appropriately set within a range not impairing the effects of the present invention, but the crystal relative to the molar amount of P in the phosphoric acid reacted with the crystalline calcium silicate. It is preferable to blend so that the value of the molar ratio (atomic ratio) of Ca in the porous calcium silicate is about 16.67 to 1.67.
(Iii) “Determine the mixing ratio of inorganic substance and phosphoric acid”
The blending ratio of the phosphoric acid to be reacted with the inorganic substance may be appropriately set within a range not impairing the effects of the present invention. However, Ca in the inorganic substance relative to the molar amount of P in the phosphoric acid to be reacted with the inorganic substance or The molar ratio (atomic ratio) of Mg is about 1.0 (monetite and brushite composition) to 1.67 (hydroxyapatite composition) in the case of Ca, and 1.0 (phosphorus in the case of Mg). It is preferable to blend so as to have a magnesium oxyhydrogen composition) to 1.5 (magnesium phosphate composition).

Moreover, the aspect (procedure) with which crystalline calcium silicate and an inorganic substance are made to react with phosphoric acid in presence of water is not limited. For example,
(1) A mode in which a mixture containing crystalline calcium silicate, an inorganic substance, and water is prepared, and phosphoric acid is added thereto while stirring the mixture,
(2) Phosphoric acid is added to the mixture A obtained by adding phosphoric acid to the mixture containing crystalline calcium silicate and water while stirring the mixture A containing inorganic substance and water. A mixture B obtained by preparing the mixture B and the mixture A and the mixture B are further mixed;
(3) To a mixture A obtained by adding phosphoric acid to a mixture containing crystalline calcium silicate and water while stirring, a mixture containing an inorganic substance and water is prepared and mixed to obtain A mode in which phosphoric acid is added thereto while stirring the resulting mixture C;
(4) To a mixture B obtained by adding phosphoric acid to a mixture containing an inorganic substance and water while stirring, a mixture containing crystalline calcium silicate and water is prepared and mixed to obtain An embodiment in which phosphoric acid is added thereto while stirring the resulting mixture D;
(5) After preliminarily determining the total amount of the crystalline calcium silicate, the inorganic substance and the phosphoric acid in accordance with the procedures (i) to (iii), the total amount is used up, and the above (1) to ( In each reaction mode of 4), a mode in which at least one of crystalline calcium silicate, inorganic substance and phosphoric acid is divided and added at two or more timings,
(6) After preliminarily determining the total amount of the crystalline calcium silicate, inorganic substance and phosphoric acid in proportions according to the above procedures (i) to (iii), the above total amount is used up, and the above (1) to ( The aspect which combines 2 or more types of 5), etc. are mentioned.

  As a dehydration molding method in the case of a molded body for a heat insulating material, an existing dehydration molding method such as press dehydration molding, papermaking method, roll dehydration molding method, centrifugal molding method, extrusion molding method, and mold injection method can be used.

  As drying methods, existing drying methods such as air drying, heat drying, hot air drying, vacuum drying, freeze drying, vacuum freeze drying, humidity control drying, controlled atmosphere substitution type drying, and supercritical drying can be used. The degree (moisture content) can be appropriately set according to the composition, purpose and application of the molded body (heat insulating material).

  The composition for a heat insulating material of the present invention is obtained by reacting a specific crystalline calcium silicate and an inorganic substance with phosphoric acid in the presence of water, and is a heat insulating material using a conventional crystalline calcium silicate as a raw material. The heat insulating property is improved as compared with the composition for materials, and it is obtained by a production method that is simple and free from the problem of calcium salt drainage. The composition for a heat insulating material of the present invention and the molded body for a heat insulating material obtained by molding the composition are useful as a practical heat insulating material having improved heat insulating properties.

  The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the examples.

  In the following, the amounts of Ca, Mg, and P in the raw materials used were analyzed in advance using a fluorescent X-ray analyzer (manufactured by Rigaku Corporation, ZSX Primus II), and the blending ratio was calculated.

Example 1
Mix ferrosilicon dust forcedly dispersed in water with quick lime that has been dehydrated in 12 times the mass of hot water so that the molar ratio (CaO / SiO ₂ ) is 1.00, and then add water. The raw slurry was prepared with a water to solid ratio of 30. This was put into an autoclave with a stirring blade (capacity: about 800 liters), reacted for 3 hours at a saturated water vapor pressure of 15 kgf / cm ² while rotating the stirring blade at a rotation speed of 29 rpm, and crystalline calcium silicate hydrate consisting of zonotlite. An aqueous slurry (also referred to as “crystalline calcium silicate hydrate slurry made of zonotlite”) containing secondary particles (particles in which primary particles (crystals) of zonotlite were aggregated) was obtained.

  Lime milk (suspension of calcium hydroxide) obtained by reducing quick lime in 12 times the mass of warm water was added to the predetermined amount of the aqueous slurry thus obtained to obtain a mixed aqueous slurry. Here, the addition amount of the lime milk was such an amount that the ratio (atomic ratio) of the molar amount of Ca in the lime milk to the molar amount of Ca in the sorted aqueous slurry was 0.667. .

  The mixed aqueous slurry is heated to 70 ° C. and stirred to add an aqueous solution of 10% phosphoric acid to react with the aqueous slurry containing the product of composition B consisting of zonotolite, hydroxyapatite and amorphous silica. A slurry was obtained. Here, the addition amount of the phosphoric acid aqueous solution is a total amount (amount A + amount B) of the amount A and the amount B, and is an amount specified as follows.

  The amount A is such that the ratio (atomic ratio) of the molar amount of Ca in the crystalline calcium silicate hydrate slurry composed of the above-mentioned zonotlite to the molar amount of P in the phosphoric acid aqueous solution Ca / P = 2.78. . In addition, when the amount A is calculated on the assumption that the calcium salt of phosphoric acid to be produced is hydroxyapatite, 60% of Ca in the crystalline calcium silicate hydrate slurry comprising the above-mentioned zonotlite reacts with phosphoric acid. It corresponds to.

  The amount B is an amount that gives a ratio (atomic ratio) Ca / P = 1.67 of the molar amount of Ca in the lime milk added to the molar amount of P in the aqueous phosphoric acid solution. Further, the amount B corresponds to an amount in which 100% of Ca in the added lime milk reacts with phosphoric acid when the calcium salt of phosphoric acid to be produced is calculated as hydroxyapatite.

  The product (composition B) is an X-ray diffractometer (manufactured by Shimadzu Corporation, powder X-ray diffractometer XRD-6100, X-ray tube: Cu (1.54060 mm), tube voltage: 40.0 kV, tube current: 30.0 mA, speed: 2.00 degrees / minute, step width: 0.0200 degrees, counting time: 0.60 seconds, slit (DS): 1.00 degrees, slit (SS): 1.00 degrees, slit (RS): 0.30 mm). The identification conditions are the same in other examples and comparative examples.

  In carrying out Example 1, when phosphoric acid is reacted with the mixture of the crystalline calcium silicate hydrate and the lime milk, the total amount of the lime milk reacts with phosphoric acid, and an excess amount of phosphoric acid and crystals. It was confirmed in advance from the identification results of the constituent crystals by the X-ray diffractometer that the hydrated calcium silicate hydrate reacted, and the amount of phosphoric acid added was as described above.

  To a predetermined amount of the aqueous slurry containing the product of composition B (the solid content of the aqueous slurry is 94 parts by mass), 3 parts by mass of glass fiber, 3 parts by mass of pulp, and surfactant (Perex OT- manufactured by Kao Corporation) After adding and mixing P) so that it might become 5 mass% with respect to solid content of the said aqueous slurry, it spin-dry | dehydrated, and it dried at 150 degreeC, and obtained the molded object (150 mm x 50 mm x 30 mm).

  The obtained molded product was good.

Density, drying shrinkage ratio, bending strength of molded body (manufactured by Yonekura Seisakusho, universal tester YS-5D, span length 12cm, 3-point bending test), thermal conductivity (Kyoto Electronics Industries, Ltd., rapid Table 1 shows the measurement results of the measurement of the thermal conductivity at 150 ° C. using a thermal conductivity meter QTM-500. In addition, the thermal conductivity of Table 1 is represented by the amount (%) of decrease in thermal conductivity compared with that based on the thermal conductivity of Comparative Example 1. In other examples and comparative examples, the physical property measurement method and the thermal conductivity display method are the same.
<< Supplement to Example 1 >>
Moreover, when the moisture absorption / release performance in the middle humidity region was measured by JIS A 1470-1 (humidity response method) using the above molded product, “moisture absorption (12 hour value): 109 g / m ² ”, “ Moisture release (12 hour value): 83 g / m ² ”.

  Further, in order to examine the relationship between the density of the molded body and the thermal conductivity, 3 parts by mass of glass fiber is added to a predetermined amount of the aqueous slurry containing the product of composition B (solid content of the aqueous slurry is 79 parts by mass), After adding and mixing 3 parts by mass of pulp, 15 parts by mass of silicon carbide, and a surfactant (Perex OT-P, manufactured by Kao Corporation) so as to be 5% by mass with respect to the solid content of the aqueous slurry, Dehydration molding was performed under three different conditions, followed by drying at 150 ° C. to obtain three types of molded bodies (310 mm × 310 mm × 30 mm) having different densities.

Using the obtained molded body (three kinds of density 0.17 g / cm ³ , 0.20 g / cm ³ , 0.25 g / cm ³ ), the average temperature 150 ° C., 300 ° C. by GHP method (flat plate direct method) The thermal conductivity at 500 ° C. and 700 ° C. was measured. As a result, the compacts having a density of 0.17 g / cm ³ were 0.041 (W / mK), 0.052 (W / mK), 0.071 (W / mK), 0.096 ( W / mK). The compacts having a density of 0.20 g / cm ³ are 0.041 (W / mK), 0.050 (W / mK), 0.066 (W / mK), and 0.086 (W / mK) at the above temperatures, respectively. )Met. The compacts having a density of 0.25 g / cm ³ are 0.041 (W / mK), 0.048 (W / mK), 0.060 (W / mK), and 0.073 (W / mK) at the above temperatures, respectively. )Met.

Example 2
In Example 1, except that the addition amount (amount A, amount B) of the phosphoric acid aqueous solution was changed as follows, generation of a composition B composed of zonotolite, hydroxyapatite, and amorphous silica was performed in the same manner as in Example 1. An aqueous slurry containing the product was obtained. Further, a molded body was obtained in the same manner as in Example 1.

  The addition amount (amount A, amount B) of the phosphoric acid aqueous solution is as follows.

  The amount A is a ratio (atomic ratio) of the molar amount of Ca in the crystalline calcium silicate hydrate slurry made of zonotlite to the molar amount of P in the aqueous phosphoric acid solution (atomic ratio) Ca / P = 16.77. . Further, when the amount A is calculated on the assumption that the calcium salt of phosphoric acid to be produced is hydroxyapatite, 10% of Ca in the crystalline calcium silicate hydrate slurry made of zonotlite reacts with phosphoric acid. Equivalent to.

  The amount B is such that the ratio (atomic ratio) of the molar amount of Ca in the added lime milk to the molar amount of P in the aqueous phosphoric acid solution (atomic ratio) Ca / P = 1.67. Further, the amount B corresponds to an amount in which 100% of Ca in the added lime milk reacts with phosphoric acid when the calcium salt of phosphoric acid to be produced is calculated as hydroxyapatite.

  The obtained molded body was almost good.

  The measurement results of the density, drying shrinkage rate, bending strength, and thermal conductivity of the molded product are shown in Example 2 of Table 1.

Example 3
In Example 1, the amount of lime milk added when preparing the mixed aqueous slurry, and the amount of the aqueous phosphoric acid solution (amount A and amount B) used when preparing the aqueous slurry containing the product of composition B are as follows. An aqueous slurry containing a product of composition B consisting of zonotolite, hydroxyapatite, and amorphous silica was obtained in the same manner as in Example 1 except that the above was changed. Further, a molded body was obtained in the same manner as in Example 1.

  The amount of lime milk added was such that the ratio of the molar amount of Ca in lime milk to the molar amount of Ca in the collected aqueous slurry (atomic ratio) was 0.083.

  The addition amount (amount A, amount B) of the phosphoric acid aqueous solution is as follows.

  The amount A is a ratio (atomic ratio) of the molar amount of Ca in the crystalline calcium silicate hydrate slurry made of zonotlite to the molar amount of P in the aqueous phosphoric acid solution (atomic ratio) Ca / P = 2.78. . Further, when the amount A is calculated on the assumption that the calcium salt of phosphoric acid to be produced is hydroxyapatite, 60% of Ca in the crystalline calcium silicate hydrate slurry made of zonotlite reacts with phosphoric acid. Equivalent to.

  The amount B is such that the ratio (atomic ratio) of the molar amount of Ca in the added lime milk to the molar amount of P in the aqueous phosphoric acid solution (atomic ratio) Ca / P = 1.67. Further, the amount B corresponds to an amount in which 100% of Ca in the added lime milk reacts with phosphoric acid when the calcium salt of phosphoric acid to be produced is calculated as hydroxyapatite.

  The obtained molded product was good.

  The measurement results of the density, drying shrinkage rate, bending strength, and thermal conductivity of the molded product are shown in Example 3 of Table 1.

Example 4
In Example 1, the amount of lime milk added when preparing the mixed aqueous slurry, and the amount of the aqueous phosphoric acid solution (amount A and amount B) used when preparing the aqueous slurry containing the product of composition B are as follows. An aqueous slurry containing a product of composition B consisting of zonotolite, hydroxyapatite, and amorphous silica was obtained in the same manner as in Example 1 except that the above was changed. Further, a molded body was obtained in the same manner as in Example 1.

  The amount of lime milk added was such that the ratio of the molar amount of Ca in lime milk (atomic ratio) to the molar amount of Ca in the collected aqueous slurry was 1.33.

  The addition amount (amount A, amount B) of the phosphoric acid aqueous solution is as follows.

  The amount A is a ratio (atomic ratio) of the molar amount of Ca in the crystalline calcium silicate hydrate slurry made of zonotlite to the molar amount of P in the aqueous phosphoric acid solution (atomic ratio) Ca / P = 2.78. . Further, when the amount A is calculated on the assumption that the calcium salt of phosphoric acid to be produced is hydroxyapatite, 60% of Ca in the crystalline calcium silicate hydrate slurry made of zonotlite reacts with phosphoric acid. Equivalent to.

  The amount B is such that the ratio (atomic ratio) of the molar amount of Ca in the added lime milk to the molar amount of P in the aqueous phosphoric acid solution (atomic ratio) Ca / P = 1.67. Further, the amount B corresponds to an amount in which 100% of Ca in the added lime milk reacts with phosphoric acid when the calcium salt of phosphoric acid to be produced is calculated as hydroxyapatite.

  The obtained molded body was almost good.

  The measurement results of the density, drying shrinkage rate, bending strength, and thermal conductivity of the molded product are shown in Example 4 of Table 1.

Example 5
The same lime milk as in Example 1 was prepared. A predetermined amount of lime milk is heated to 70 ° C., stirred, added with a 10% phosphoric acid aqueous solution, reacted with it, then dispersed with a homomixer, containing a reaction product consisting of hydroxyapatite An aqueous slurry (1) was obtained.

  Here, the addition amount of the phosphoric acid aqueous solution was set to an amount such that the ratio (atomic ratio) Ca / P = 1.67 of the molar amount of Ca in the lime milk to the molar amount of P in the phosphoric acid aqueous solution. This amount of addition corresponds to the amount that 100% of Ca in lime milk reacts with phosphoric acid when the calcium salt of phosphoric acid to be produced is calculated as hydroxyapatite.

  A crystalline calcium silicate hydrate slurry made of the same zonotlite as in Example 1 was prepared. An aqueous solution containing a post-reaction composition consisting of hydroxyapatite and amorphous silica by heating a predetermined amount of the slurry to 70 ° C. while stirring and adding a 10% aqueous phosphoric acid solution to the reaction. A slurry (2) was obtained.

  Here, the addition amount of the phosphoric acid aqueous solution is the ratio (atomic ratio) of the molar amount of Ca in the crystalline calcium silicate hydrate slurry composed of the above-mentioned zonotlite to the molar amount of P in the aqueous phosphoric acid solution Ca / P = 1. The amount was .67. When the amount of phosphoric acid to be produced is calculated as hydroxyapatite, the amount added is such that 100% of Ca in the crystalline calcium silicate hydrate slurry made of the above-mentioned zonotlite reacts with phosphoric acid. Equivalent to.

  The aqueous slurry (1) was mixed with the aqueous slurry (2) to obtain an aqueous slurry containing a product of composition A composed of hydroxyapatite and amorphous silica. Here, the amount of the aqueous slurry (1) mixed with the aqueous slurry (2) is, as a conversion value, the mole of Ca in the lime milk relative to the molar amount of Ca in the crystalline calcium silicate hydrate slurry composed of the above-mentioned zonotlite. The amount ratio (atomic ratio) was 0.667.

  Except for the above, a molded body was obtained in the same manner as in Example 1.

  The obtained molded body was almost good.

  The measurement results of the density, drying shrinkage rate, bending strength, and thermal conductivity of the molded product are shown in Example 5 of Table 1.

Example 6
Water was added to calcium carbonate powder (Shiraishi Calcium Co., Ltd., Brilliant-1500), and a dispersion (calcium carbonate dispersion) dispersed using a homomixer was prepared. An aqueous solution containing a calcium salt of phosphoric acid (hydroxyapatite and brushite) by heating a predetermined amount of the dispersion to 70 ° C. and stirring to add a 10% aqueous phosphoric acid solution to the reaction. A slurry (1) was obtained.

  Here, the addition amount of the phosphoric acid aqueous solution was such that the ratio of the molar amount of Ca in the calcium carbonate dispersion to the molar amount of P in the phosphoric acid aqueous solution (atomic ratio) Ca / P = 1.67. . This amount of addition corresponds to the amount that 100% of Ca in the calcium carbonate dispersion reacts with phosphoric acid when the calcium salt of phosphoric acid to be produced is calculated as hydroxyapatite.

  A crystalline calcium silicate hydrate slurry made of the same zonotlite as in Example 1 was prepared. An aqueous solution containing a post-reaction composition consisting of hydroxyapatite and amorphous silica by heating a predetermined amount of the slurry to 70 ° C. while stirring and adding a 10% aqueous phosphoric acid solution to the reaction. A slurry (2) was obtained.

  Here, the addition amount of the phosphoric acid aqueous solution is the ratio (atomic ratio) of the molar amount of Ca in the crystalline calcium silicate hydrate slurry composed of the above-mentioned zonotlite to the molar amount of P in the aqueous phosphoric acid solution Ca / P = 2. The amount was .78. When the amount of phosphoric acid to be produced is calculated as hydroxyapatite, the amount added is such that 60% of Ca in the crystalline calcium silicate hydrate slurry made of the above-mentioned zonotlite reacts with phosphoric acid. Equivalent to.

  The aqueous slurry (1) was mixed with the aqueous slurry (2) to obtain an aqueous slurry containing the composition B consisting of zonotlite, calcium phosphate, and amorphous silica. Here, the amount of the aqueous slurry (1) mixed with the aqueous slurry (2) is, as a conversion value, in the calcium carbonate dispersion with respect to the molar amount of Ca in the crystalline calcium silicate hydrate slurry composed of the zonotlite. The molar amount ratio (atomic ratio) of Ca was 0.667.

  Except for the above, a molded body was obtained in the same manner as in Example 1.

  The obtained molded product was good.

  The measurement results of the density, drying shrinkage rate, bending strength, and thermal conductivity of the molded product are shown in Example 6 of Table 1.

Example 7
Water was added to Portland cement (manufactured by Ube Mitsubishi Cement Co., Ltd.), and a dispersion (Portland cement dispersion) dispersed using a homomixer was prepared. An aqueous slurry (1) containing a calcium salt of phosphoric acid (brushite) is reacted by adding a 10% strength aqueous phosphoric acid solution while stirring a predetermined amount of the dispersion to 70 ° C. and stirring. )

  Here, the addition amount of the phosphoric acid aqueous solution was such that the ratio of the molar amount of Ca in the calcium carbonate dispersion to the molar amount of P in the phosphoric acid aqueous solution (atomic ratio) Ca / P = 1.67. . This addition amount corresponds to an amount in which 100% of Ca in the Portland cement dispersion reacts with phosphoric acid when the calcium salt of phosphoric acid to be produced is calculated as hydroxyapatite.

  The same aqueous slurry (2) as in Example 6 was prepared.

  The aqueous slurry (1) was mixed with the aqueous slurry (2) to obtain an aqueous slurry containing the composition B consisting of zonotlite, calcium phosphate, and amorphous silica. Here, the amount of the aqueous slurry (1) mixed with the aqueous slurry (2) is, as a conversion value, the Ca in the Portland cement dispersion with respect to the molar amount of Ca in the crystalline calcium silicate hydrate slurry made of zonotlite. The molar amount ratio (atomic ratio) was 0.513.

  Except for the above, a molded body was obtained in the same manner as in Example 1.

  The obtained molded product was good.

  The measurement results of the density, drying shrinkage rate, bending strength, and thermal conductivity of the molded product are shown in Example 7 in Table 1.

Example 8
CSH aqueous slurry (obtained by using lime milk, ferrosilicon dust and water as raw materials, blending so that CaO / SiO ₂ = 1.00 and reacting at 90 ° C. for 1.5 hours with stirring) was prepared. . A predetermined amount of the CSH aqueous slurry is heated to 70 ° C., and while stirring, a 10% concentration phosphoric acid aqueous solution is added and reacted. Then, the mixture is dispersed with a homomixer, and hydroxyapatite and amorphous silica are used. An aqueous slurry (1) containing the post-reaction composition was obtained.

  Here, the addition amount of the phosphoric acid aqueous solution was such that the ratio of the molar amount of Ca in the CSH aqueous slurry to the molar amount of P in the phosphoric acid aqueous solution (atomic ratio) Ca / P = 1.67. This amount of addition corresponds to the amount that 100% of Ca in the CSH aqueous slurry reacts with phosphoric acid when the calcium salt of phosphoric acid to be produced is calculated as hydroxyapatite.

  The same aqueous slurry (2) as in Example 6 was prepared.

  The aqueous slurry (1) was mixed with the aqueous slurry (2) to obtain an aqueous slurry containing a product of composition B consisting of zonotlite, hydroxyapatite, and amorphous silica. Here, the amount of the aqueous slurry (1) mixed with the aqueous slurry (2) is, as a conversion value, the amount of Ca in the CSH aqueous slurry with respect to the molar amount of Ca in the crystalline calcium silicate hydrate slurry made of zonotlite. The molar ratio (atomic ratio) was 0.385.

  Except for the above, a molded body was obtained in the same manner as in Example 1.

  The obtained molded product was good.

  Table 8 shows the measurement results of the density, drying shrinkage rate, bending strength, and thermal conductivity of the molded body.

Example 9
A dispersion (talc dispersion) in which water was added to talc powder (Nihon Talc Co., Ltd., Microace P-3) was prepared. While stirring a predetermined amount of the talc dispersion at room temperature (20 ° C.), a 10% concentration phosphoric acid aqueous solution was added thereto and reacted at 200 ° C. for 4 hours. The product was washed with water, filtered, and phosphoric acid. An aqueous slurry (1) containing magnesium hydrogen and unreacted talc was obtained.

  Here, the addition amount of the phosphoric acid aqueous solution was such that the ratio of the molar amount of Mg in the talc dispersion to the molar amount of P in the phosphoric acid aqueous solution (atomic ratio) Mg / P = 1.50. This addition amount corresponds to an amount in which 100% of Mg in the talc dispersion reacts with phosphoric acid when the magnesium salt of phosphoric acid to be produced is calculated as magnesium phosphate.

  The same aqueous slurry (2) as in Example 6 was prepared.

  The aqueous slurry (1) is mixed with the aqueous slurry (2), and an aqueous slurry containing a product of composition D consisting of zonotolite, hydroxyapatite, amorphous silica, magnesium hydrogen phosphate and unreacted talc is prepared. Obtained. Here, the amount of the aqueous slurry (1) mixed with the aqueous slurry (2) is, as a conversion value, the amount of Mg in the talc dispersion relative to the molar amount of Ca in the crystalline calcium silicate hydrate slurry made of zonotolite. The molar ratio (atomic ratio) was 0.398.

  Except for the above, a molded body was obtained in the same manner as in Example 1.

  The obtained molded product was good.

  Table 9 shows the measurement results of density, drying shrinkage, bending strength, and thermal conductivity of the molded body.

Example 10
A dispersion was prepared by adding water to magnesium hydroxide powder (manufactured by Kinsei Matec Co., Ltd.). While stirring a predetermined amount of the magnesium hydroxide dispersion at room temperature (20 ° C.), a 10% strength aqueous phosphoric acid solution was added thereto and reacted at 200 ° C. for 4 hours. An aqueous slurry (1) containing magnesium hydrogen phosphate was obtained.

  Here, the addition amount of the phosphoric acid aqueous solution is such that the ratio of the molar amount of Mg in the magnesium hydroxide dispersion to the molar amount of P in the aqueous phosphoric acid solution (atomic ratio) Mg / P = 1.50. did. This addition amount corresponds to an amount in which 100% of Mg in the magnesium hydroxide dispersion reacts with phosphoric acid when the magnesium salt of phosphoric acid to be produced is calculated as magnesium phosphate.

  The same aqueous slurry (2) as in Example 6 was prepared.

  The aqueous slurry (1) was mixed with the aqueous slurry (2) to obtain an aqueous slurry containing a product of composition B consisting of zonotlite, hydroxyapatite, amorphous silica, and magnesium hydrogen phosphate. Here, the amount of the aqueous slurry (1) mixed with the aqueous slurry (2) is, as a conversion value, in the magnesium hydroxide dispersion with respect to the molar amount of Ca in the crystalline calcium silicate hydrate slurry made of zonotolite. The molar amount ratio (atomic ratio) of Mg was 0.762.

  Except for the above, a molded body was obtained in the same manner as in Example 1.

  The obtained molded product was good.

  Table 10 shows the measurement results of the density, drying shrinkage rate, bending strength, and thermal conductivity of the molded body.

Example 11
An aqueous slurry obtained by adding 25 times the mass of water to a powder (tobermorite powder TK, manufactured by Nippon Insulation Co., Ltd.) consisting of secondary particles of crystalline calcium silicate hydrate composed of tobermorite (hereinafter referred to as “ Also referred to as “crystalline calcium silicate hydrate slurry made of tobermorite”.

  The same amount of lime milk as in Example 1 was added to a predetermined amount of the aqueous slurry thus obtained to obtain a mixed aqueous slurry. Here, the addition amount of the lime milk is an amount such that the ratio (atomic ratio) of the molar amount of Ca in the lime milk to the molar amount of Ca in the sorted aqueous slurry is 0.75. .

  The mixed aqueous slurry is heated to 70 ° C. and stirred, and a 10% strength aqueous phosphoric acid solution is added and reacted with the resulting aqueous slurry containing composition B composed of tobermorite, hydroxyapatite, and amorphous silica. Obtained. Here, the addition amount of the phosphoric acid aqueous solution is a total amount (amount A + amount B) of the amount A and the amount B, and is an amount specified as follows.

  The amount A is a ratio (atomic ratio) of the molar amount of Ca in the crystalline calcium silicate hydrate slurry made of tobermorite to the molar amount of P in the aqueous phosphoric acid solution (atomic ratio) Ca / P = 2.78. . Further, when the amount A is calculated on the assumption that the calcium salt of phosphoric acid to be produced is hydroxyapatite, 60% of Ca in the crystalline calcium silicate hydrate slurry composed of tobermorite reacts with phosphoric acid. It corresponds to.

  The amount B is an amount that gives a ratio (atomic ratio) Ca / P = 1.67 of the molar amount of Ca in the lime milk added to the molar amount of P in the aqueous phosphoric acid solution. Further, the amount B corresponds to an amount in which 100% of Ca in the added lime milk reacts with phosphoric acid when the calcium salt of phosphoric acid to be produced is calculated as hydroxyapatite.

  In carrying out Example 11, when phosphoric acid is reacted with the mixture of the crystalline calcium silicate hydrate and the lime milk, the entire amount of lime milk reacts with phosphoric acid, and an excess amount of phosphoric acid and crystals. It was confirmed in advance from the identification results of the constituent crystals by the X-ray diffractometer that the hydrated calcium silicate hydrate reacted, and the amount of phosphoric acid added was as described above.

  Except for the above, a molded body was obtained in the same manner as in Example 1.

  The obtained molded product was good.

  The measurement results of the density, drying shrinkage rate, bending strength, and thermal conductivity of the molded product are shown in Example 11 of Table 1.

Example 12
A crystalline calcium silicate hydrate slurry made of the same zonotlite as in Example 1 was prepared. The same calcium carbonate dispersion as in Example 6 was added to a predetermined amount of the slurry to obtain a mixed aqueous slurry. Here, the amount of the calcium carbonate dispersion added is the ratio (atomic ratio) of the molar amount of Ca in the calcium carbonate dispersion to the molar amount of Ca in the crystalline calcium silicate hydrate slurry made of the zonotlite. The amount was 0.667.

  Aqueous slurry containing composition C consisting of calcium carbonate, hydroxyapatite and amorphous silica by adding 10% aqueous phosphoric acid solution to the mixed aqueous slurry while heating to 70 ° C. and stirring. Got. Here, the addition amount of the phosphoric acid aqueous solution is a total amount (amount A + amount B) of the amount A and the amount B, and is an amount specified as follows.

  The amount A is such that the ratio (atomic ratio) of the molar amount of Ca in the crystalline calcium silicate hydrate slurry composed of the above-mentioned zonotlite to the molar amount of P in the phosphoric acid aqueous solution Ca / P = 2.78. . In addition, when the amount A is calculated on the assumption that the calcium salt of phosphoric acid to be produced is hydroxyapatite, 60% of Ca in the crystalline calcium silicate hydrate slurry comprising the above-mentioned zonotlite reacts with phosphoric acid. It corresponds to.

  The amount B is such that the ratio (atomic ratio) of the molar amount of Ca in the calcium carbonate dispersion to the molar amount of P in the aqueous phosphoric acid solution (atomic ratio) Ca / P = 1.67. Further, the amount B corresponds to an amount in which 100% of Ca in the added calcium carbonate dispersion reacts with phosphoric acid when it is calculated that the calcium salt of phosphoric acid to be produced is hydroxyapatite.

  Except for the above, a molded body was obtained in the same manner as in Example 1.

  The obtained molded product was good.

  The measurement results of the density, drying shrinkage rate, bending strength, and thermal conductivity of the molded product are shown in Example 12 of Table 1.

Example 13
In Example 1, except that the water to solid content ratio was changed from 30 to 24, a crystalline calcium silicate hydrate slurry made of zonotlite (hereinafter referred to as “crystalline calcium silicate water made of zonotlite”). Also referred to as “Japanese slurry (2)”.

  To a predetermined amount of the hydrate slurry (2), the same lime milk as in Example 1 and a dispersion obtained by adding water to Portland cement (manufactured by Ube Mitsubishi Cement Co., Ltd.) (Portland cement dispersion) are added, and water is added. A mixed aqueous slurry comprising Japanese slurry (2), lime milk and Portland cement was obtained.

  Here, the amount of lime milk added was such that the ratio of the molar amount of Ca in lime milk (atomic ratio) to the molar amount of Ca in hydrate slurry (2) was 0.331. The amount of Portland cement dispersion added is such that the ratio (atomic ratio) of the molar amount of Ca in the Portland cement dispersion to the molar amount of Ca in the hydrate slurry (2) is 0.036. It was.

  The mixed aqueous slurry is heated to 70 ° C. and stirred while adding a 10% strength aqueous phosphoric acid solution to react, thereby containing a product of composition B consisting of zonotolite, hydroxyapatite, and amorphous silica. An aqueous slurry was obtained. Here, the addition amount of the phosphoric acid aqueous solution is a total amount (amount A + amount B + amount C) of the amount A, the amount B, and the amount C, and is an amount specified as follows.

  The amount A is such that the ratio (atomic ratio) of the molar amount of Ca in the hydrate slurry (2) to the molar amount of P in the aqueous phosphoric acid solution (atomic ratio) Ca / P = 1.84. Further, the amount A corresponds to the amount that 95% of Ca in the hydrate slurry (2) reacts with phosphoric acid when the calcium salt of phosphoric acid to be produced is calculated as hydroxyapatite.

  The amount B is an amount that gives a ratio (atomic ratio) Ca / P = 1.67 of the molar amount of Ca in the lime milk added to the molar amount of P in the aqueous phosphoric acid solution. Further, the amount B corresponds to an amount in which 100% of Ca in the added lime milk reacts with phosphoric acid when the calcium salt of phosphoric acid to be produced is calculated as hydroxyapatite.

  The amount C is such that the ratio (atomic ratio) Ca / P = 1.67 of the molar amount of Ca in the added Portland cement dispersion to the molar amount of P in the phosphoric acid aqueous solution. Further, the amount C corresponds to an amount in which 100% of Ca in the added Portland cement dispersion reacts with phosphoric acid when the calcium salt of phosphoric acid to be produced is calculated as hydroxyapatite.

  In a predetermined amount of the obtained aqueous slurry (solid content of the aqueous slurry is 79 parts by mass), 15 parts by mass of silicon carbide, 3 parts by mass of glass fiber, 3 parts by mass of pulp, surfactant (Sanyo Chemical Industries, Ltd.) Sanmorin OT-70) is 3% by mass based on the solid content of the aqueous slurry, and the flocculant (manufactured by Hakuto Co., Ltd., Hacrok AU) is 0.1% by mass based on the solid content of the aqueous slurry. After being added and mixed, it was dehydrated and dried at 150 ° C. to obtain a molded body (150 mm × 50 mm × 30 mm). The molded product was good.

  Table 13 shows the measurement results of the density, drying shrinkage rate, bending strength, and thermal conductivity of the molded body.

Example 14
From the hydrate slurry (2) and Portland cement, the same Portland cement dispersion as in Example 13 was added to a predetermined amount of the crystalline calcium silicate hydrate slurry (2) comprising the same zonotlite as in Example 13. A mixed aqueous slurry was obtained.

  Here, the addition amount of the Portland cement dispersion is such that the ratio (atomic ratio) of the molar amount of Ca in the Portland cement dispersion to the molar amount of Ca in the hydrate slurry (2) is 0.276. The amount to be.

  The mixed aqueous slurry is heated to 70 ° C. and stirred, and a 10% strength aqueous phosphoric acid solution is added thereto to cause a reaction. An aqueous slurry containing the composition B consisting of zonotolite, hydroxyapatite, and amorphous silica is prepared. Obtained. Here, the addition amount of the phosphoric acid aqueous solution is a total amount (amount A + amount B) of the amount A and the amount B, and is an amount specified as follows.

  The amount A is such that the ratio of the molar amount of Ca in the hydrate slurry (2) to the molar amount of P in the aqueous phosphoric acid solution (atomic ratio) Ca / P = 2.78. Further, the amount A corresponds to the amount that 60% of Ca in the hydrate slurry (2) reacts with phosphoric acid when the calcium salt of phosphoric acid to be produced is calculated as hydroxyapatite.

  The amount B is such that the ratio (atomic ratio) of the molar amount of Ca in the added Portland cement dispersion to the molar amount of P in the aqueous phosphoric acid solution (atomic ratio) Ca / P = 1.67. Further, the amount B corresponds to an amount in which 100% of Ca in the added Portland cement dispersion reacts with phosphoric acid when the calcium salt of phosphoric acid to be produced is calculated as hydroxyapatite.

  15 parts by mass of silicon carbide, 4 parts by mass of glass fiber, 3 parts by mass of pulp, 1 part by mass of Portland cement, and a flocculant in a predetermined amount of the obtained aqueous slurry (solid content of the aqueous slurry is 77 parts by mass) (Hakuto Co., Ltd., Hakuflock AU) was added and mixed so as to be 0.1% by mass with respect to the solid content of the aqueous slurry, dehydrated, dried at 150 ° C., and molded (150 mm × 50 mm). × 30 mm) was obtained. The molded product was good.

  The measurement results of the density, drying shrinkage rate, bending strength, and thermal conductivity of the compact are shown in Example 14 of Table 1.

Example 15
A crystalline calcium silicate hydrate slurry (2) comprising the same zonotlite as in Example 13 was prepared. A predetermined amount of the hydrate slurry (2) is heated to 70 ° C. and stirred, and a 10% strength phosphoric acid aqueous solution is added thereto to react with it, and is composed of zonotolite, hydroxyapatite, and amorphous silica. An aqueous slurry was obtained.

  Here, the addition amount of the phosphoric acid aqueous solution is the ratio of the molar amount of Ca in the hydrate slurry (2) to the molar amount of P in the aqueous phosphoric acid solution (atomic ratio) Ca / P = 2.38. The amount. This addition amount corresponds to an amount in which 70% of Ca in the hydrate slurry (2) reacts with phosphoric acid when it is calculated that the calcium salt of phosphoric acid produced is hydroxyapatite.

  The same lime milk as in Example 1 was added to the obtained aqueous slurry to obtain a mixed aqueous slurry composed of zonotolite, hydroxyapatite, amorphous silica, and lime milk.

  Here, the added amount of lime milk is such that the ratio (atomic ratio) of the molar amount of Ca in lime milk to the molar amount of Ca in the aqueous slurry composed of the above-mentioned zonotlite, hydroxyapatite and amorphous silica is 0.00. The amount was set to 668.

  An aqueous slurry containing a product of composition B consisting of zonotolite, hydroxyapatite, and amorphous silica by heating the mixed aqueous slurry to 70 ° C. while stirring and adding a 10% aqueous phosphoric acid solution to react. Got.

  Here, the addition amount of the phosphoric acid aqueous solution was set so that the ratio (atomic ratio) of the molar amount of Ca in the added lime milk to the molar amount of P in the phosphoric acid aqueous solution was Ca / P = 1.67. . This amount of addition corresponds to the amount that 100% of Ca in the added lime milk reacts with phosphoric acid when the calcium salt of phosphoric acid to be produced is calculated as hydroxyapatite.

  In a predetermined amount of the obtained aqueous slurry (the solid content of the aqueous slurry is 78 parts by mass), 15 parts by mass of silicon carbide, 4 parts by mass of glass fiber, 3 parts by mass of pulp, and a surfactant (Sanyo Chemical Industries, Ltd.) Manufactured by NAROACTY CL-100) 2% by mass with respect to the solid content of the aqueous slurry, and flocculant (Hakuto AU, manufactured by Hakuto Co., Ltd.) is 0.2% by mass with respect to the solid content of the aqueous slurry. (Hakuto Co., Ltd., Hakutron Z-152) is 0.1% by mass with respect to the solid content of the aqueous slurry, and antifoaming agent (Kao Corporation, Antifoam E-20) is 0% with respect to the aqueous slurry After adding and mixing so that it might become 0.01 mass%, it spin-dry-molded and dried at 150 degreeC, and the molded object (150mmx50mmx30mm) was obtained. The molded product was good.

  Table 15 shows the measurement results of the density, drying shrinkage rate, bending strength, and thermal conductivity of the molded body.

Example 16
A molded body was obtained in the same manner as in Example 13 except that Portland cement was replaced with alumina cement (AGC Ceramics Co., Ltd., Asahi Fondage (AF)). The molded product was good.

  The measurement results of the density, drying shrinkage rate, bending strength, and thermal conductivity of the molded product are shown in Example 16 of Table 1.

Comparative Example 1
A crystalline calcium silicate hydrate slurry made of the same zonotlite as in Example 1 was prepared. A molded body was obtained in the same manner as in Example 1 except that lime milk was not added and phosphoric acid was not added. The molded body was slightly deformed by drying shrinkage.

  The measurement results of the density, drying shrinkage rate, bending strength, and thermal conductivity of the compact are shown in Comparative Example 1 in Table 1.

Claims (14)

1) at least one crystalline calcium silicate selected from the group consisting of zonotlite, tobermorite, gyrolite and wollastonite; 2) calcium hydroxide, calcium carbonate, cement, amorphous calcium silicate hydrate, talc the density of and and at least one inorganic material selected from the group consisting of magnesium hydroxide, the obtained by reacting the phosphoric acid that the cross-sectional thermal material composition in the presence of water, for a thermal insulator formed body There 0.1 to 0.3 g / obtained by dehydrating formation and drying so that the cm ^3, for a thermal insulator shaped body density of 0.1 to 0.3 g / cm ^3. The said composition for heat insulating materials is for heat insulating materials of Claim 1 containing the composition A containing the at least 1 sort (s) of phosphate of calcium salt of phosphoric acid and magnesium salt of phosphoric acid, and amorphous silica. Molded body . The said composition for heat insulating materials contains the composition B which added the at least 1 sort (s) of crystalline calcium silicate selected from the group which consists of a zonotlite, a tobermorite, a gyrolite, and a wollastonite to the said composition A to Claim 1 The molded object for heat insulating materials as described. The composition for a heat insulating material contains at least one inorganic substance selected from the group consisting of calcium hydroxide, calcium carbonate, cement, amorphous calcium silicate hydrate, talc and magnesium hydroxide in the composition A. The molded object for heat insulating materials according to claim 1, comprising the added composition C. The composition for a heat insulating material includes at least one crystalline calcium silicate selected from the group consisting of zonotlite, tobermorite, gyrolite and wollastonite in the composition A, and calcium hydroxide, calcium carbonate, cement, The molded object for heat insulating materials according to claim 1, comprising a composition D to which at least one inorganic substance selected from the group consisting of amorphous calcium silicate hydrate, talc and magnesium hydroxide is added. The said crystalline calcium silicate is a molded object for heat insulating materials in any one of Claims 1-5 which is a secondary particle of the crystalline calcium silicate hydrate containing at least 1 sort (s) of a zonotolite and a tobermorite. The molded body for a heat insulating material according to any one of claims 1 to 6, wherein the inorganic substance is calcium hydroxide. The said inorganic substance is the molded object for heat insulating materials in any one of Claims 1-6 which are calcium hydroxide and cement. 1) at least one crystalline calcium silicate selected from the group consisting of zonotlite, tobermorite, gyrolite and wollastonite; 2) calcium hydroxide, calcium carbonate, cement, amorphous calcium silicate hydrate, talc and at least one inorganic material selected from the group consisting of magnesium hydroxide, after obtaining by the reacting with phosphoric acid Ridan thermal material composition in the presence of water, the composition for the heat-insulating material The molded product for heat insulating material having a density of 0.1 to 0.3 g / cm ³ is dehydrated and dried so that the density of the molded product for heat insulating material is 0.1 to 0.3 g / cm ^3. Manufacturing method . The said crystalline calcium silicate is a manufacturing method of Claim 9 which is a secondary particle of the crystalline calcium silicate hydrate containing at least 1 sort (s) of a zonotolite and a tobermorite. The manufacturing method according to claim 9 or 10 , wherein the inorganic substance is calcium hydroxide. The manufacturing method according to claim 9 or 10 , wherein the inorganic substance is calcium hydroxide and cement. The crystalline calcium silicate and containing the water the inorganic material mixture was prepared to obtain the heat-insulating material composition by adding phosphoric acid thereto while stirring the mixture, any of claims 9-12 The manufacturing method of crab. Phosphoric acid was added to the mixture A obtained by adding phosphoric acid while stirring the mixture containing the crystalline calcium silicate and water, and the mixture containing the inorganic substance and water was stirred. a mixture B obtained by preparing, obtaining the thermal insulator composition by further mixing the mixture a and mixture B, the process according to any one of claims 9-12.