WO2004005215A1

WO2004005215A1 - Calcium silicate hardened article

Info

Publication number: WO2004005215A1
Application number: PCT/JP2003/008480
Authority: WO
Inventors: Akihiro Ogawa; Hiroyoshi Matsuyama
Original assignee: Asahi Kasei Kabushiki Kaisha
Priority date: 2002-07-03
Filing date: 2003-07-03
Publication date: 2004-01-15
Also published as: TWI227702B; JP4343108B2; DE10392839B4; GB2405402A; TW200402395A; CN1780800A; AU2003246260A1; GB2405402B; GB0427475D0; CN100352786C; JPWO2004005215A1; DE10392839T5

Abstract

A calcium silicate hardened article which has a flexural strength of 0.05 MPa or more, a heat conductivity of 0.02 to 0.1 Wm-1K-1, and an air permeability of 5 X 10-4 to 1 m2h-1Pa-1 or less, and exhibits dynamic insulating property.

Description

0

Description Calcium silicate cured product Technical field

The present invention relates to a cured calcium silicate having dynamic thermal insulation. More specifically, the flexural strength is not less than 0.05 MPa, the thermal conductivity is from 0.02 to 0.1 l Wm— ¹ , and

Permeability is 5 X 1 0 - ⁴ ~ A in lm ² hi P a ¹ or less, about calcium silicate hardened body showing the dynamic insulation properties. The hardened calcium silicate of the present invention is required to have not only light weight and high strength, but also nonflammability, and also have high heat insulation and high air permeability, and therefore have dynamic heat insulation. It can be used advantageously as a wall material for construction. “Dynamic heat insulation” means a property that exhibits high air permeability and a heat insulation effect, and a building wall material having dynamic heat insulation is designed ventilation.

(Always keep the air in the room fresh by constantly or regularly ventilating the air) and at the same time reduce the energy loss by the dynamic insulation method (hereinafter referred to as “the method”). It can be used advantageously for the “dynamic adiabatic method”. Further, the present invention relates to a method for producing the above-mentioned cured product of calcium silicate. JP2003 / 008480

Conventional technology

With the death of fossil fuels, air pollution due to the use of fossil fuels in large quantities, and global warming caused by carbon dioxide, as major social issues, the need for energy conservation is increasing more and more. Above all, the energy consumption of houses and buildings has been increasing as the desire for a comfortable living space using air conditioning and heating has increased, and efforts have been made to conserve energy by making buildings highly insulated and airtight. Have been. However, since air quality deteriorates due to daily activities in a closed space due to high thermal insulation and high airtightness, dehumidifiers, humidifiers, and air purifiers are required to maintain a clean state. Has been used.

As a result, the effect on energy conservation has been lost. For this reason, in recent years, planned ventilation (by always or periodically providing ventilation to keep the room air fresh) is required for buildings with high insulation and high airtightness. Design and materials that have both functions of heat insulation and ventilation are required.

On the other hand, it has been found that there is a structural limit to reducing the heat transfer coefficient on the walls and ceilings of buildings, and that there is a limit to reducing thermal energy loss.

Under such circumstances, the dynamic insulation method (hereinafter referred to as the “dynamic insulation method”), which can simultaneously perform planned ventilation while reducing heat energy loss, has been adopted in Scandinavian countries. Researched in mind. The dynamic insulation method is a method in which outside air is introduced into a room through heat insulating material in a wall or ceiling to recover heat loss from the wall or ceiling. In this method, the air introduced into the room through the insulation is fresh and is supplied into the room while being warmed in the wall. As a result, air supply preheating is realized and the indoor high air quality is maintained while reducing the apparent heat transmission rate.

In order to achieve an effective dynamic insulation method, a material that has both high heat insulation and excellent air permeability is required. In addition, there is a need for materials that are easy to construct, are inexpensive, and have high strength. In addition, materials are required to be nonflammable from the viewpoint of fire resistance requirements.

Conventionally, organic foam-based heat insulating materials have been used as heat insulating materials. However, organic foam-based heat insulating materials have a high closed cell rate and thus have low air permeability and are not suitable for the dynamic heat insulating method. There is also a problem with incombustibility. As an inorganic heat insulating material, there is a foam glass obtained by foaming glass, but it is expensive, and has a high percentage of closed cells, and thus has a low air permeability and is not suitable for a dynamic heat insulating material. Also

WO 02/066693 and Japanese Patent Application Laid-Open Publication No. 2001-1226784 disclose techniques relating to a cured product of calcium silicate. However, calcium silicate hardened obtained by these techniques is disclosed. The body has low air permeability and does not function as dynamic insulation.

In the conventional thermal insulation method, waste paper pulp is mainly used. ■ Inorganic fibers such as crushed materials and rock wool are divided into a certain range and filled into a frame. As a result, there was a problem that the thermal conductivity of the form itself was higher than that of the heat insulating material, so that heat was generated through the form and the effectiveness of dynamic insulation could not be fully exhibited. In addition, there was a problem in that heat insulation had to be applied to an unnecessarily thick thickness due to the heat loss caused by the gap between the mold and the heat insulating powder generated when the heat insulating material was injected.

Wood-cement board / concrete block, which has been conventionally used as a building material, has a bulk specific gravity of 0.5 or more, and therefore has a large heat conductivity and a large heat energy loss due to heat conduction. Therefore, there was a problem that the effect of the dynamic insulation could not be sufficiently exhibited. Also, Japanese Patent Application Publication No. JP-A-2001-3482883 discloses a technology of a sound absorbing material. However, since the bulk specific gravity is around 0.35 and the thermal conductivity is large, dynamic Not suitable as thermal insulation.

Also, the use of rock wool ports / glass mats with low thermal conductivity has been considered. However, even if it is called a board or a mat, it is not a hardened body, but only a cotton or a fibrous fiber intertwined. Therefore, the bending strength is low, and beams and frames are required at the time of construction. Therefore, there is a problem that heat conduction occurs from itself, and the effectiveness of dynamic insulation cannot be obtained. In addition, many fine fibers, which are considered harmful when cutting on site, The health of workers. Furthermore, since the air permeability is too high, it cannot be used alone as a dynamic heat insulator, and a plastic sheet with many fine holes must be placed indoors. Not only the construction becomes complicated, but also the non-combustibility of the whole heat insulating material is reduced.

In view of the above situation, the present inventors have intensively studied to solve the above-mentioned problems of the prior art. As a result, surprisingly, at least one aluminum compound selected from the group consisting of siliceous raw materials, cement, aluminum sulfate and its hydrate, and other sulfur compounds, and In some cases, a foaming agent is added to an aqueous slurry of a solid mixture composed of calcareous raw materials and having a specific composition, and the aqueous slurry containing the foaming agent is injected into a mold and pre-cured. In the method for obtaining a hardened calcium silicate by autoclaving, the weight ratio of the water Z solid mixture in the aqueous slurry is adjusted to 0.6 or less, or the weight ratio is adjusted. When it exceeds 0.6, the bending strength is reduced to 0 by adding at least two members selected from the group consisting of a surfactant, a viscosity modifier and an antifoaming agent to the aqueous slurry. 0 5MPa or more, heat transfer The rate is 0 0 2 ~ 0 · l W m- and permeability is 5 X 1 0 -. ⁴ ~ A is ^¹ m ² h- 1 P a 1 or less, silicotungstic showing the dynamic insulation properties It has been found that a hardened calcium acid product can be obtained. The above-mentioned cured product of calcium silicate is required to have not only light weight and high strength but also nonflammability, and also to have dynamic heat insulating properties because it has both high heat insulating properties and high air permeability. It can be used advantageously as a wall material for buildings. The present invention has been completed based on this finding.

Accordingly, an object of the present invention is not only to be lightweight and high-strength, but also to be non-flammable, and to have high heat insulation and high air permeability, and therefore to have dynamic heat insulation. An object of the present invention is to provide a hardened calcium silicate that can be advantageously used as a required building wall material.

Another object of the present invention is to provide a method for efficiently producing the above-mentioned cured product of calcium silicate.

The above and other objects, features and advantages of the present invention will become apparent from the following detailed description and the appended claims, taken in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE FIGURES

1 and 2 are X-ray powder diffraction data of the cured calcium silicate of Example 13 and X-ray diffraction diagrams showing a method of calculating Ia and Ib. In each of the drawings, CPS means coutntspersecond.

Figure 1: Powder X-ray diffraction of cured calcium silicate of Example 13 Data and Ia [the lowest value of the diffraction intensity in the angle region between the two diffraction peaks of the (220) plane and the (222) plane of tobermorite], and Ib [ FIG. 2 is an X-ray diffraction diagram showing a method for calculating the diffraction peak intensity of the (220) plane.

Fig. 2: Powder X-ray diffraction data of the cured product of calcium silicate of Example 13 and I (220) [diffraction peak intensity of (220) plane of tobermorite], I (002) [ Tobermorite's

FIG. 6 is an X-ray diffraction diagram showing a method for calculating the (002) plane diffraction peak intensity].

FIG. 3 is a schematic explanatory view showing one example of an apparatus used for measuring the air permeability defined in the present invention. Explanation of reference numerals

1 sample

2 Sample holder with rubber

3 Vacuum pump

Pressure regulating valve

5 Pressure adjustment tank

6 Differential pressure gauge

7 Detailed description of the invention

That is, according to one aspect of the present invention, (1) The bending strength is more than 0.05MPa,

(2) The thermal conductivity is between 0.02 and 0.1 l Wm! ! — ¹ , and

(3) The air permeability is 5 X 10 _ ⁴ or more: L m ² hiP a ¹ or less,

A cured calcium silicate exhibiting dynamic thermal insulation is provided.

Next, in order to facilitate understanding of the present invention, first, basic characteristics and preferred embodiments of the present invention will be listed.

1. (1) The bending strength is more than 0.05MPa,

(2) thermal conductivity of 0.02 to 0.1 Wm— and

(3) Air permeability is 5 X 10 — ⁴ or more; Lm ² h ¹ or less,

Calcium silicate cured product showing dynamic heat insulation.

2. The cured product of calcium silicate as described in 1 above, wherein the thermal conductivity is 0.02 to 0.08 Wm- ¹ or less.

3. The cured product of calcium silicate as described in 1 above, wherein the thermal conductivity is 0.02 to 0. O e Wm- ¹ : ^ ^-1 or less.

4. It consists mainly of tobermorite, and the diffraction peak intensity Ib of the (220) plane of topamolites in powder X-ray diffraction is higher than that of (2220) and (222) planes of tobermorite. ) Two diffractions on the surface 4. The cured calcium silicate according to any one of items 1 to 3, wherein the cured product has a relationship of IbZla3 with the lowest value Ia of the diffraction intensity in the angle region sandwiched by the peaks.

5. A method for producing a hardened calcium silicate, comprising the following steps (1) to (4).

(1) Providing an aqueous slurry comprising water and a solid mixture, wherein the solid mixture is substantially at least selected from the group consisting of siliceous raw materials, cement, aluminum sulfate and hydrates thereof. It consists of one aluminum compound, another sulfuric acid compound and, in some cases, calcareous raw materials.

The amount of the aqueous in Sula rie of the aluminum compound, the terms of oxide (A 1 ₂ O ₃₎ 0 by weight of the solid mixture in. 0 9-1 0% by weight, and other sulfuric acid compound The amount in the aqueous slurry, including the aluminum sulfate or the hydrate thereof, is 0.15 to 15% by weight based on the weight of the solid mixture in terms of SO ₃ ,

The weight ratio of the water to the solid mixture is 2.3 to 5.5;

The weight ratio of the calcareous raw material to the cement is 0.6 or less.

(2) Add a foaming agent to the aqueous slurry.

(3) Inject the aqueous slurry into a mold. (4) After the aqueous slurry is pre-cured, it is cured by autoclaving.

6. The foaming agent is at least one member selected from the group consisting of aluminum powder and an aqueous slurry containing aluminum, and the foaming agent is added to the weight of the solid mixture in terms of solids. The method according to the above item 5, characterized in that it is used in an amount of 0.03 to 0.95% by weight.

7. A method for producing a cured product of calcium silicate, comprising the following steps (1) to (4).

(1) An aqueous slurry containing water and a solid mixture is provided, wherein the solid mixture is substantially selected from the group consisting of siliceous raw materials, cement, aluminum sulfate and hydrates thereof. Both consist of one aluminum compound, other sulfate compounds and, in some cases, calcareous raw materials.

The amount of the aqueous in Sula rie of the aluminum compound, the 0.0 9-1 0% by weight, and other sulfuric acid compound relative to the weight of the solid mixture in terms of oxide (A 1 ₂ 0 ₃₎ the amount in the aqueous Sula rie is the rather also the aluminum sulfate including their hydrates, than zero. 1 5 to 1 5 wt% der relative to the weight of the solid mixture with S 0 ₃ weight basis ,

A weight ratio of the water to the solid mixture of 2.3 to 5.5; Yes,

The weight ratio of the calcareous raw material to the cement exceeds 0.6.

(2) Add a foaming agent to the aqueous slurry.

(3) Inject the aqueous slurry into a mold.

(4) After pre-curing the aqueous slurry, it is autoclaved. '

However, at least two members selected from the group consisting of a surfactant, a viscosity modifier and an antifoaming agent are added to the aqueous slurry, and at this time, the viscosity modifier and the antifoamer are added. Is added after step (1) and before step (2), and the surfactant is added simultaneously with the addition of the foaming agent in step (2).

8. The foaming agent is at least one foaming agent selected from the group consisting of aluminum powder and an aluminum-containing aqueous slurry, and the foaming agent is converted to a solid mixture in terms of solids. 8. The method according to the above item 7, characterized in that it is used in an amount of 0.03 to 0.95% by weight based on the weight of the compound.

9. The surfactant is at least one compound selected from the group consisting of higher alcohol sulfates, higher alcohol sodium sulfate and polyoxyethylene alkyl ether; The surfactant is added to the solid equivalent weight of the foaming agent. The method according to the above item 7 or 8, characterized in that 0.01 to 200% by weight is used.

10. The viscosity modifier is at least one compound selected from the group consisting of methylcell monopolyvinyl alcohol, wherein the viscosity modifier is based on the weight of the solid mixture. 0.1 to 1% by weight or less. 10. The method according to any one of claims 1 to 9.

11. The antifoaming agent is at least one compound selected from the group consisting of silicones, fatty acids, fatty acid ester alcohols, and phosphoric acid esters, wherein the defoaming agent is The preceding paragraph characterized by using 0.001 to 3% by weight based on the weight of the mixture? The method according to any one of claims 1 to 10. The “calcium silicate cured product” of the present invention is a general term for a material containing a calcium silicate compound and having an arbitrary shape obtained by curing, and is generally a concrete, a cured mortar, a lightweight foamed material. Concrete (hereinafter often referred to as “ALC”), fiber reinforced calcium silicate board (carbon board), etc.

The calcium silicate cured product of the present invention,

(1) The bending strength is more than 0.05MPa,

(2) thermal conductivity 0. 0 2 ~ 0. 1 W m- 1 K _ 1 and, (3) When the air permeability is 5 X 10 — ⁴ to lm ² hi Pa ¹ or less,

Shows dynamic thermal insulation. Therefore, the cured product of calcium silicate of the present invention can be advantageously used as a dynamic heat insulator. Here, the dynamic insulation is a material used in the dynamic insulation method. For the dynamic insulation method, see, for example, B. J. Taylor et.

al., Analytic l Investigation of the Steady-State Behavior of Dynamic and Diffusive Building

Envelopes (Building and Environment, Vol. 31, No. 6, p. 519-525, 1996), and “Research on Multifunctional Insulation Technology” (Survey Report No. 53, Housing in Hokkaido, Japan) Urban Research Institute, 1993) can be referred to. In the dynamic thermal insulation method, planned ventilation can be performed at the same time while reducing thermal energy loss. In other words, the indoor heat lost to the outside from the side wall and ceiling wall is recovered inside the side wall and ceiling wall by introducing outside air into the room through the heat insulating material in the side wall and ceiling wall, and the outside air is It is assumed that it will be supplied indoors while being heated inside the body. Furthermore, the air introduced into the room through the insulation is excellent not only in recovering heat loss but also in being fresh. As a result, air supply preheating is achieved while reducing the apparent heat transmission rate, and high indoor air quality is maintained.

The cured product of calcium silicate of the present invention has a flexural strength of 0.05 Mpa or more, preferably 0.07 Mpa or more, and more preferably 0.1 Mpa or more. If the bending strength is less than 0.05 MPa, it becomes difficult to maintain a suitable panel shape as a dynamic heat insulating material, and workability is reduced.

The cured product of the calcium silicate of the present invention preferably has a thermal conductivity of 0.02 to 0.1 Wm— ¹ , more preferably 0.02 to 0.08 Wm—. The range is from 0 to ¹ , particularly preferably from 0.02 to 0. O e Wm- ¹ ! ^ — ¹ . If the thermal conductivity exceeds 0.1 W m — ¹ K- ¹ , the heat insulation performance will decrease, and the wall itself will be used to obtain a sufficient heat insulation effect when using a cured calcium silicate as a heat insulating material. The thickness must be increased, which causes problems in workability. Further, the lower limit of the thermal conductivity of the cured product of calcium silicate of the present invention is 0.02 Wm- ¹ from a practical viewpoint.

Calcium silicate hardened product of the present invention, the ventilation rate of 5 X 1 0 one ^{4 ~: lm S h - ipa} - 1 a is and this is rather preferable, rather preferably Ri good is 1 X 1 0 - ³ ~ 0 5 m ² h— i P a — ¹ , particularly preferably 5 X 10 — ³ to 0.1 m ² h- ¹ P a — ¹ or less. When the permeability is in the above range, when the calcium silicate cured body is used as a dynamic heat insulating material, a substantial reduction in heat transmission rate and ventilation can be realized. Permeability is 5 X 1 0 - If less than ⁴ m ² h one ¹ P a- ^1, does not function as a dynamic insulation material can not and this Komu Ri taken outside air and ventilation performance is lost . For example, The WO O 2/0 6 6 9 3 silicate months Rushiumu cured product obtained by the method described in the ventilation rate ^{^{5 X 1 0 - 4 m 2}} h - for ¹ P a ¹ is less than, dynamic insulation It does not function as a material. Further, when the passing air ratio is more than lm ² h- a ^1, only a Ri faster the flow velocity of the air, it is difficult to perform supply preheating. Also, if the air permeability is too high, the pressure differential across the wall will be small, and it will not be possible to create sufficient airflow required for dynamic insulation.

Specifically, in the present invention, the side surfaces of the cylindrical sample (length L, cross-sectional area S) of the calcium silicate cured body except for both end surfaces are sealed with epoxy resin, and both ends of the sample are dried using a vacuum pump. When the differential pressure across the sample is 1 kPa, the flow rate of the air flowing through the sample is measured, and the value calculated by equation (1) is defined as the air permeability.

Ventilation rate ^{^{(m 2 ~ 1 P a "}} 1)

= W X L Z S / A P (1)

W: Air flow rate (mSh- ¹ )

L: Length of sample (m)

S: Cross section of sample (m ² )

ΔP: Pressure difference (P a) A method for measuring the air permeability will be described below with reference to FIG. The sample 1 is set in the sample holder 2 having a rubber packing which can be compressed by compressed air on the inner surface. The pressure in the pressure adjustment tank 5 is controlled by the pressure adjustment valve 4 using the vacuum pump 3 and the flow rate of the air flowing into the sample when the differential pressure measured by the differential pressure gauge 6 is 1 kPa. Is measured by flow meter 7. From the obtained flow rate, the air permeability is calculated by the above equation (1). The cured product of calcium silicate of the present invention is mainly composed of tobermorite (5Ca a · 6Sio2 · 5H, O), which is observed in powder X-ray diffraction. The ratio (I b) of the diffraction peak intensity I b to the minimum value I a of the diffraction peak intensity I b in the angle region between the diffraction lines (2 0 0) and (0 2 2) of the two tobermorites / I a) is preferably 3 or more, more preferably 4 or more. Here, X-ray powder diffraction refers to powder X-ray diffraction using CuΚα-rays as X-rays.

Whether or not tobermorite is the main component in the cured calcium silicate of the present invention is determined as follows by using both a scanning electron microscope observation and a powder X-ray observation of the fracture surface of the cured calcium silicate. To judge.

First, in X-ray powder diffraction, there is no other diffraction peak exceeding the strongest line (220) of tobermorite. However, when crystalline silica, calcium carbonate, and gypsum coexist with tobermorite, tobermorite is mainly used. Nevertheless, due to the high crystallinity of these coexisting substances, the strongest line of these substances may exceed the strongest line of tobermorite. Secondly, using a scanning electron microscope, the fractured surface was coarsened by a foaming agent (described later) in the area of the microscope's set magnification of 250,000 times and 35.41 mx 18.9 m. The matrix other than the bubble portion was randomly observed at 20 points, and if the average area ratio where plate- or strip-shaped tobermorite particles were observed was 50% or more, tobermorite was mainly used. It consists of Further, the average of the area ratio is preferably 60% or more, and more preferably 80% or more. Here, the coarse bubble portion refers to the region around the coarse bubble and about 5 m from the coarse bubble, and a region where tobermorite is easily generated due to the free space. However, even in such a case, in powder X-ray diffraction, a highly crystalline coexisting substance other than tobermorite with respect to the diffraction peak intensity Ib of the (220) plane of tobermorite, that is, crystalline silica, carbonate The ratio (IcZIb) of the diffraction intensity Ic of the strongest line of calcium and gypsum is preferably 3 or less, and more preferably 2 or less. Here, the plate-like or strip-like particles refer to the plate-like or strip-like tobermorite particles observed at the microscope setting magnification of 250 × as described above, and the microscope setting magnification of 500 ×. Observed at 0x, the distance between two surfaces almost parallel to each other in one particle is equivalent to the minimum length of the particle (hereinafter referred to as “thickness”). And the maximum length of the particle is more than 5 times the minimum length. Of course, the maximum length and thickness here are the projected lengths in two dimensions. The size of the particles of these tobermorites is not particularly limited, but it is preferable that the maximum length be a few ^ m to 10 ^ m.

Usually, tobermorite often coexists with low crystalline calcium silicate hydrate (hereinafter abbreviated as CSH). It is known that CSH takes various particle forms. However, since it usually takes a fibrous, granular, or massive particle form, it can be clearly distinguished from non-tobermorite particles under an electron microscope. Such CSH can be contained within a range that does not destroy the basic skeleton of tobermorite. However, CSH may reduce various required properties for building materials such as strength, weather resistance, and durability. If a large amount of CSH is present in the hardened calcium silicate, the dimensional stability during repeated wet and dry operations is reduced. When left in the air for a long time, these CSH easily react with carbon dioxide contained in the air to cause a carbonation reaction that decomposes into calcium carbonate and amorphous silicic acid. At this time, cracks and structural deterioration occur due to volume shrinkage. Therefore, even if it is determined by X-ray diffraction and electron microscopy that it mainly consists of tobermorite, it is preferable that CSH is not contained as much as possible.

As described above, CSH particles were obtained under the electron microscope under Tobermorite It is easily determined that they are not particles. However, because CSH takes various particle forms, it may not be clearly distinguishable from other trace coexisting substances, such as fibrous gypsum and particulate calcium carbonate, by electron microscopic observation. For this reason, it is difficult to determine the CSH content ratio using an electron microscope. X-ray powder diffraction of the cured product in which tobermorite and CSH coexist shows that a broad region was found between the (220) diffraction peak and the (222) diffraction peak of tobermorite. CSH diffraction peaks are observed. This diffraction peak of CSH usually appears around 29.1 to 29.4 ° (20). When the amount of CSH is smaller than that of tobermorite, the diffraction peak of CSH becomes a form absorbed by the diffraction lines of tobermorite, and it is usually impossible to measure the diffraction intensity of CSH.

However, when a large amount of CSH is present, the diffraction intensity of X-rays in the region between the (220) diffraction peak and the (222) diffraction peak of tobermorite is larger than that of the knock ground. Therefore, it is possible to determine whether a large amount of CSH is present. When the hardened calcium silicate does not contain CSH at all and is mainly composed of high crystalline tobermorite, the lowest value of the X-ray intensity in the same region coincides with the background intensity.

On the other hand, even if CSH is not present, if the crystallinity of tobermorite is low, Ib '/ Ia will be small. This This is because (220) and (222) are close to each other, and the peaks of the peaks overlap. When the crystallinity of tobermorite is low, the strength of the cured calcium silicate and the weather resistance are reduced.

Therefore, the diffraction peak intensity of the (220) plane of tobermorite

1b, two tobermorite diffraction lines, (2 2 0) and (2

22 The larger the ratio (Ib / Ia) of the diffraction intensity to the minimum value Ia in the angle region sandwiched by 2), the smaller the CSH contained in the hardened calcium silicate or the higher the tobermorite Has high crystallinity. Here, the intensities Ia and Ib are values including the background intensity, and the method of calculating Ia and Ib is shown in FIG.

The cured product of the low specific gravity calcium silicate of the present invention has the diffraction peak intensity I of the (002) plane, which is the diffraction peak of the (220) plane, among the diffraction peaks of tobermorite observed in powder X-ray diffraction. The ratio (I (002) / I (220)) to the intensity I (220) is preferably 0.25 or more, and more preferably 0.25.

30 or more. Plate-shaped or strip-shaped particles of tobermorite are considered to have the direction perpendicular to the plane, that is, the thickness direction, as the C-axis direction of the crystal. Therefore, an increase in the relative intensity of I (002) means an increase in the relative regularity in the C-axis direction, and accordingly, an increase in the thickness of the plate-like crystal. . JCPDS (Joint Committee on Powder Dif fraction Standard) According to the card No. 1 9 — 1 364, the ideal tobermorite crystal I (002) / I (220) is described as 0.8. As the value approaches, the thickness of the crystal increases and the strength of the single crystal increases. As a result, the strength of the cured body composed of these crystals also increases. The calculation method of these I (002) and I (220) is shown in Fig. 2.I (002) is the diffraction angle around 6 to 9 ° (2Θ), and the back ground is This is the true diffraction intensity obtained by linear approximation, and I (220) is the true diffraction intensity obtained by linearly approximating the background over a diffraction angle of around 20 to 40 ° (20). Is the diffraction intensity.

The hardened calcium silicate of the present invention preferably has a bulk specific gravity of 0.05 to 0.25, more preferably 0.05 to 0.2, and particularly preferably 0.5 to 0.2. 0 5 to 0.18. The bulk specific gravity as used herein refers to the bulk specific gravity when dried at 105 ° C for 24 hours, that is, the absolute specific gravity.

The cured calcium silicate of the present invention may or may not substantially contain air bubbles, but preferably contains air bubbles. Foam refers to a foaming agent that uses a surfactant that is used in the foam-preform method and is made using aluminum powder as a foaming agent, which has been conventionally used in the manufacture of lightweight foam concrete. Refers to bubbles created using

The cured product of calcium silicate of the present invention contains bubbles. In this case, it is preferable to have pores in the part (matrix) that forms the skeleton other than the bubbles. It is also preferable that the thickness of the matrix between the bubbles is small.

The cured calcium silicate of the present invention can be advantageously used as a building wall material such as the above-mentioned dynamic heat insulating material, ordinary heat insulating material, and sound absorbing material. Regarding the shape when used as a building wall material as described above, it is preferable to have a panel shape, and the size and thickness are not particularly limited as long as the panel shape can be maintained. . By having the shape of the panel, it is easy to secure the airtightness required for the dynamic insulation technology, and the construction is simplified.

Hereinafter, the method for producing the cured calcium silicate of the present invention will be described.

The cured product of calcium silicate of the present invention can be produced by a method comprising the following steps (1) to (4).

(1) An aqueous slurry containing water and a solid mixture is provided, wherein the solid mixture is substantially selected from the group consisting of siliceous raw materials, cement, aluminum sulfate and hydrates thereof. It is composed of one aluminum compound, other sulfate compounds and, in some cases, calcareous raw materials.

The amount of the aqueous in Sula rie of the aluminum compound, the 0.0 9-1 0% by weight, and other sulfuric acid compound relative to the weight of the solid mixture in terms of oxide (A 1 ₂ 〇 ₃₎ The aqueous slurry The amount in the Li one is, is rather also the aluminum sulfate including their hydrates, than zero. 1 5 to 1 5 wt% der relative to the weight of the solid mixture with S 0 ₃ amount conversion,

The weight ratio of the water to the solid mixture is 2.3 to 5.5;

The weight ratio of the calcareous raw material to the cement is 0.6 or less.

(2) Add a foaming agent to the aqueous slurry.

(3) Inject the aqueous slurry into a mold.

(4) After the aqueous slurry is pre-cured, it is cured by autoclaving.

In the present invention, the siliceous material, S i 0 content ₂ 7 0 wt% or more, say a raw material containing metal oxides such as aluminum oxide and with the remaining ingredients. For example, crystalline silica stone, silica sand, quartz, and rocks with high content thereof, diatomaceous earth, silica fume, fly ash, natural clay minerals, and fired products thereof. Among these, crystalline siliceous raw materials are silica stone, silica sand, quartz, and rocks with a high content of them, such as powder X-rays, single quartz or list barite in diffraction. A substance that exhibits a sharp diffraction peak. The amorphous silicic acid raw material refers to diatomaceous earth, silica fume, fly ash, etc., which do not show a distinctive diffraction peak in powder X-ray diffraction. In the present invention, the cement refers to a cement mainly composed of a silicate component and a calcium component, such as ordinary portant cement, early-strength portant cement, and belite cement. Moreover, quicklime and calcareous material (C a O) 5 0 wt% or more, slaked lime and the remaining components (C a (OH) _2), carbonate Karushiu arm (C a C_〇 ₃₎ the raw material, including is there.

Et al is, in the present invention, the aluminum sulfate, I匕学formula _{_{(A 1 2 (SO 4)}} 3) or refers to Ranaru material, and hydrates thereof e.g., the formula (A 1 ₂ (S 〇 ₄ ) Refers to a compound containing water of crystallization as shown in 3 · 17H ₂₀ ). It is a raw material form powder, but may be any Sula rie, while excluding the water of crystallization _{_{(A l 2 (S 0 4}} ) 3) and to use those containing 8 0 wt% or more. The addition amount of aluminum sulfate is also rather its hydrates, 0 in terms of oxide (A 1 ₂ O 3) relative to the total weight of the solid mixture. Than zero 9-1 0% by weight Dea, rather then preferred Is from 0.2 to 10% by weight, more preferably from 0.5 to 8% by weight.

It is found in, and other sulfate compounds, rather name in particularly limited, any compound containing S 〇 ₃ or S 〇 ₄ Bayoi. For example, sulfite, sulfate, ₍₄ C a S 0) anhydrite, gypsum (C a S 〇 ₄ 2 H ₂ 〇.), Hemihydrate gypsum _{(C a SO 4 - 1/} 2 H 2 0) , such as Hydrate of gypsum, alkali such as magnesium sulfate, etc.Sulfate of earth metal, sodium sulfate, etc. Sulphate of metal sulfates, metal sulphates such as copper sulphate and silver sulphate, etc., which may be used alone or in combination, but are preferably gypsum or dihydrate Hydrates are used. The addition amount of other acid compounds of that is 0 relative to the total weight of rather also sulfuric aluminum of the solid mixture with S 〇 ₃ terms including their hydrates 1 5 ~:. In L 5 wt% And preferably from 0.2 to 10% by weight.

Further, the weight ratio of the calcareous raw material to cement is preferably 0.6 or less, more preferably 0.4 or less, particularly in terms of oxide (CaO conversion). Is less than 0.3. Even when the weight ratio of the calcareous raw material to the cement exceeds 0.6, the aqueous slurry is selected from the group consisting of a surfactant, a viscosity modifier and an antifoaming agent. By adding at least two of them, the cured calcium silicate of the present invention can be obtained. At that time, the addition of the viscosity modifier and the antifoaming agent is performed after the step (1) and before the step (2), and the addition of the surfactant is performed in the step (2). And simultaneously with the addition of Incidentally, even when the weight ratio of the calcareous raw material to the cement is 0.6 or less, a surfactant, a viscosity modifier, an antifoaming agent and the like may be added in the same manner.

The above-mentioned surfactants include anionic surfactants such as higher alcohol sulfates or higher alcohol sodium sulfate, and non-ionic surfactants such as polyoxygen. Ethylene alkyl ether and the like, in an amount of 0.01 to 200% by weight based on the weight of the foaming agent in terms of solids, and more preferably 0.1 to: L 0. % By weight.

The above-mentioned viscosity modifier is at least one selected from the group consisting of methylcellulose and polyvinyl alcohol, and the amount of addition is 0.01 to 1% by weight based on the weight of the solid mixture. Yes, more preferably from 0.02 to 0.5% by weight.

Antifoaming agents include dimethyl silicone, silicone such as alkyl-modified silicone in which the methyl group is substituted with a hydrocarbon having 2 or more carbon atoms, fatty acids such as glycerin fatty acid, and glycerin fatty acid ester. And fatty acid esters such as sucrose fatty acid esters, higher alcohols such as octyl alcohol, and phosphoric esters such as aromatic phosphates and aliphatic phosphates. In addition,

, Especially dimethyl silicone and alkyl-modified silicone are preferably used, and the amount of addition is 0.01 to 3% by weight, preferably 0.00, based on the weight of the solid mixture. It is between 5 and 2% by weight, more preferably between 0.01 and 2% by weight.

Further, in the method of the present invention, the weight ratio of water to the weight of the solid mixture (water Z solids ratio) needs to be 2.3 to 5.5. If this ratio is less than 2.3, a molded article having a bulk specific gravity aimed at by the present invention cannot be obtained, and the heat conductivity tends to increase. If it exceeds 5.5, when the aqueous slurry is poured into a mold, the solid raw material and water are separated, and a molded body tends not to be obtained.

In the present invention, the foaming agent is an aluminum powder or the like generally used in a lightweight cellular concrete. The addition form of the aluminum powder is not particularly limited, and the addition form usually used for producing a lightweight cellular concrete can be used, and the aluminum powder is added in the powder state. Method, in order to improve the dispersibility, separate the part of the water to be used in advance, mix the aluminum powder with the water and add it as aluminum slurry, lightweight air bubbles For example, a method of adding an aluminum base for producing concrete (see US Pat. No. 4,318,270) can be used. Here, the term “aluminum slurry” refers to a dispersion of aluminum powder in water. The concentration of the aluminum powder in the aluminum slurry is 0.1 to 50% by weight, preferably 1 to 30% by weight, more preferably 2 to 10% by weight with respect to water. It is. The amount of the foaming agent to be added is from 0.03 to 0.95% by weight, preferably from 0.05 to 0.7% by weight, based on the total weight of the solid mixture in terms of solids of the foaming agent. More preferably, it is 0.08 to 0.5% by weight. The ratio of the volume after foaming to the slurry of the raw material is preferably from 1.5 to 4.0, more preferably from 2.0 to 3.5, and particularly preferably from 2.0 to 3.5. Or 2.5 to 3.5. All ingredients used in the manufacturing method of the present invention, the molar ratio S i 0 ₂ of C a O contained in the raw material (C a O / S i 0 2) is from 0.5 to 1.1 is Shi preferred More preferably, they are mixed in an aqueous slurry state so as to be 0.6 or more and less than 1.0.

In producing the cured calcium silicate of the present invention, it is preferable that 50% by weight or more of the siliceous raw material used is crystalline. The crystalline siliceous raw material is preferably fine silica powder having a specific surface area of at least 500 cm ² Zg, more preferably at least 700 cm ² Zg. Even if the finely divided silica stone is too fine, it is more difficult to handle it. Therefore, it is preferable that the fineness of the fine silica stone is not more than 300,000 cm ² Zg as measured by the Blaine specific surface area.

In the method for producing a cured calcium silicate of the present invention, at least one aluminum compound selected from the group consisting of siliceous raw materials, cement, aluminum sulfate and hydrates thereof is substantially used. An aqueous slurry containing a solid mixture of sulphate, other sulphate compounds and, if appropriate, calcareous raw materials is stirred. The aqueous slurry temperature is preferably from 40 ° C to 100 ° C, more preferably from 50 ° C to 80 ° C. The stirring time is preferably 2 minutes or more, more preferably 10 minutes or more. Mixing of these solid mixtures with aqueous slurries containing water involves the use of mixers commonly used in industry. However, a stirrer having high-speed rotating blades for low-viscosity mortar, for example, a paddle mixer having a baffle plate in a stirring tank is preferably used.

In the production method of the present invention, when a calcareous raw material is used, if all of the calcareous raw material is mixed simultaneously with the siliceous raw material and the cement, the calcareous raw material may delay the initial hydration of the cement. Therefore, if it is desired to accelerate pre-curing, the components of the solid mixture other than the calcareous raw material and water, or the solid mixture containing a part of the calcareous raw material and water should be in a slurry state at 40 to 100 ° C. After performing the first step of mixing for at least 10 minutes and less than 5 hours at a temperature of 40 to 100 ° C., preferably adding all of the calcareous material or the remainder of the calcareous material. It is also preferable to use a method of performing a second step of mixing in 30 seconds or more and within 1 hour, more preferably 1 minute or more and 30 minutes or less, and then pouring into a mold and pre-curing. Here, when the raw materials are charged, the addition to the aqueous slurry in the first first step is the primary charge, and the addition to the aqueous slurry in the second step is the second charge, and thereafter. Name.

The above aluminum compound is preferably added in the first step together with the other solid mixture components and water, and mixed at 40 to 100 ° C for 10 minutes or more and less than 5 hours.

The viscosity adjusting agent and the defoaming agent may be added at any time as long as they are before the foaming agent is added, but are preferably added immediately after the solid mixture is charged. Also, the surfactant is foaming Add surfactant to aqueous slurry at the same time as adding surfactant. The foaming agent is preferably added after the above-mentioned solid mixture is charged, and the stirring time after adding the foaming agent is preferably 10 seconds or more and 3 minutes or less, and 20 seconds or more and 1 minute. Within is more preferred. If the time is less than 10 seconds, the foaming agent does not disperse uniformly, and coarse bubbles tend to be generated due to the coalescence of the bubbles. If the time exceeds 3 minutes, the foaming agent reacts during stirring, which tends to cause coalescence and defoaming.

The calcium silicate cured product of the present invention can also be obtained by a preform method. That is, a method of forming a foam by blowing air into a foaming agent or an aqueous solution thereof and mixing the foam with the above-mentioned aqueous slurry (Japanese Patent Application Laid-Open No. 63-29554) A method of mixing a foaming agent with an aqueous slurry and then forming a foam with a foaming machine is preferably used. However, in the preform method, it is necessary to add a viscosity modifier and an antifoaming agent, and the amount of addition is the same as when a foaming agent is used. Here, as the foaming agent, those conventionally used in this field can be used, and the type thereof is not particularly limited. Examples thereof include a synthetic surfactant-based foaming agent and a resin soap-based foaming agent. And hydrolyzed protein foaming agents.

The cured product of calcium silicate of the present invention preferably contains 0.1 to 3.0% by weight of a water-repellent substance. The method for imparting water repellency using a water repellent substance is not particularly limited. However, it is preferable to develop a high water contact angle of 100 ° or more, for example, by a vapor deposition method.

The water-repellent substance is not particularly limited. For example, siloxane compounds, alkoxysilane compounds, fatty acids, fatty acid salts, epoxy resins, urethane resins, silicone resins, vinyl acetate resins, It is a water-repellent substance such as a resin resin or a resin emulsion such as a styrene-butadiene resin, and one or a mixture of two or more thereof can be used. Among them, siloxane compounds, that is, silicone oils in which part of the methyl groups of polydimethylsiloxane or polydimethylsiloxane are replaced with hydrogen, phenyl groups, trifluoropropyl groups, or the like, and alkoxysilane compounds, It is more preferable to use an alkylalkoxysilane compound such as methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, or isobutyltriethoxysilane. The content of the water-repellent substance is preferably from 0.1 to 3.0% by weight, and more preferably from 0.5 to 2% by weight. If it is less than 0.1% by weight, water repellency cannot be expected, and if it is more than 3.0% by weight, strength decreases.

The hardened calcium silicate of the present invention can also contain a small amount of reinforcing fiber, light aggregate, resin, etc. within a range that does not affect the physical properties. Reinforcing fibers are preferably used to increase the strength. Reinforcement fibers here are alkali-resistant glass fibers, It is an inorganic fiber such as carbon fiber, stainless steel fiber, ceramic fiber, and asbestos fiber, and an organic fiber such as aramid fiber, vinylon fiber, polypropylene fiber, and pulp fiber. One type or a mixture of two or more types can be used. In order to obtain the desired reinforcing performance of the cured calcium silicate, it is preferable to use aramide fiber, alkali-resistant glass fiber, and carbon fiber, and furthermore, use para-aramid fiber. Is preferred. In addition, pulp fibers are preferably used because they are inexpensive, and finely ground pulp is particularly preferably used. Although the fiber length of the reinforcing fiber is not particularly limited, it is preferably 1 to 20 mm, more preferably 3 to 10 mm, and more preferably, from the viewpoint of reinforcing performance and formability. It is preferably between 5 and 8 mm. Although the content of the reinforcing fiber is not particularly limited, it is preferably 0.05 to 3 vol%, more preferably 0.1 to 3 vol% with respect to the volume of the cured body including the voids. ~ 2 vol%. If it is less than 0.05 vol%, the desired reinforcing effect cannot be obtained, while if it exceeds 3 Vo 1%, the fibers are entangled during mixing and fiber-like lumps are likely to be formed. However, uniform dispersion in the cured product becomes difficult. The lightweight aggregate is, for example, shirasu balloon or pearlite, and may be any material that is generally used to reduce the weight of concrete. The amount of the lightweight aggregate is not particularly limited, but is preferably 0.1 to 30% by weight based on the weight of the solid mixture. It is preferably 1 to 20% by weight. The resin is preferably a resin having heat resistance, such as a phenol resin or a resole resin. The amount of the resin to be added is not particularly limited, but is 0.1 to 30% by weight or less, preferably 1 to 20% by weight or less based on the weight of the solid mixture.

The aqueous slurry thus mixed is mixed with a water-repellent substance or a reinforcing fiber as necessary, and the mixture is directly poured into a mold and molded. At this time, if necessary, it is poured into a formwork in which a reinforcing steel bar or a reinforcing wire mesh is arranged to be formed. At this time, it is preferable that the reinforcing steel bar or the reinforcing wire mesh has been subjected to a waterproof treatment. The aqueous slurry injected into the mold is pre-cured by self-heating or external heating, preferably at 40 to 100 ° C for 1 to 48 hours or more. . Preliminary hardening is preferably performed in an environment where moisture evaporation is suppressed, such as in a steam curing room. The obtained pre-cured body is cut into an arbitrary shape as needed, and then cured at high temperature and pressure using an autoclave. For cutting, a method generally used for manufacturing lightweight cellular concrete, for example, a wire cutting method can be used. The conditions of the autoclave are above 160 ° C (gauge pressure: about 5.3 kgf / cm ² ) and 220 ° C (gauge pressure: about 22.6 kgf / cm ² ). cm ² ) The following is preferred. The obtained cured product is dried to obtain the calcium silicate cured product of the present invention. The thus obtained cured product of calcium silicate according to the present invention has high heat insulating properties and air permeability, so that it can be used as a suitable dynamic heat insulating material. Further, the cured calcium silicate of the present invention is most suitable as a dynamic heat insulating material because it is easy to construct, inexpensive, has high strength, and is nonflammable.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

In the following examples and comparative examples, various measurement methods adopted are as follows.

[Thermal conductivity]

The thermal conductivity was measured at a low temperature plate of 5 ° C and a high temperature plate of 35 ° C according to the plate heat flow meter method of JIS A1412. The shape of the test piece was 200 × 200 mm, the thickness was 25 mm, and the weight became constant under the conditions of a temperature of 20 ° C. and a humidity of 60%.

[Ventilation rate]

The measurement was performed by the following method using the apparatus shown in FIG. Cylindrical sample 1 (Cross-sectional area (S) = 50 mm, length

(L)-50 mm), except for the sides at both ends, were sealed with epoxy resin, and set on a sample holder 2 having a rubber packing on the inner surface that could be pressed with compressed air. The pressure in the pressure regulating tank 5 is controlled by the pressure regulating valve 4 using the vacuum pump 3, and when the differential pressure measured by the differential pressure gauge 6 is 1 kPa, the flow rate of the air flowing into the sample is reduced. Measured by flow meter 7

It was calculated by (1). Ventilation rate (m ² h- ipa E)

= W X L / S / A P (1)

W: Air flow rate (m ³ h—

L: Length of sample (m)

S: Cross section of sample (m ² )

ΔP: Pressure difference (P a) The sample used had a constant weight at a temperature of 20 ° C. and a humidity of 60%.

[Bending strength, compression strength]

Place the cured product in a constant temperature / humidity bath at 20 ° C and 60% relative humidity (RH), and measure the cured product when the water content reaches 10 ± 2% based on the absolute dry condition. It was used as a test sample. The measurement was performed according to the measurement of bending strength and compressive strength of JISR5201. That is, the test piece dimensions used for the bending strength measurement were 40 mm × 40 mm × 60 mm, and the span width was 100 mm. The maximum load was measured on a pressurized surface of 40 mm X 40 mm on half of the test piece cracked in the bending test, and this was taken as the compressive strength. [Bulk specific gravity]

The bulk specific gravity was calculated from the weight and size (volume) of the cured product having the same dimensions as those subjected to the bending test after curing in the autoclave and dried at 105 ° C for 24 hours. .

[Powder X-ray diffraction: Measurement of Ia and Ib]

After pulverizing the sample used in the bending strength test in a mortar, the X-ray diffractometer (RINT 2000; manufactured by Rigaku Denki Co., Ltd., Japan) is used to obtain the above-mentioned diffraction peak of Cu K line. The strength Ib and the minimum value Ia were determined. The measurement conditions are as follows: acceleration voltage of 40 kV, acceleration current of 200 mA, light receiving slit width of 0.15 mm, scanning speed of 4 ° / min, and sampling of 0.2 °. The X-ray diffraction lines were monochromatic and counted by the monochromator on the graph item.

The minimum value of the diffraction intensity including the background in the angle region between the two tonolight diffraction lines (220) and (222) is Ia, and the background is Let I b be the maximum intensity of the tobermorite diffraction line (2 0) including. Note that these two diffraction lines correspond to the diffraction lines near 29.0 ° and 30.0 ° (2 °), respectively. Figure 1 shows a schematic diagram of the calculation method.

[Powder X-ray diffraction: Measurement of I (002) and I (220)] The sample and the measurement conditions were the same as in the above-mentioned measurement of Ia and Ib. Where I (002) is the diffraction angle of 6 to 9 °

It is the true diffraction intensity obtained by linearly approximating the background over (2Θ). Similarly, I (220) is the true diffraction intensity obtained by linearly approximating the knock ground over a diffraction angle of around 20 to 40 ° (2 °). Note that the (002) diffraction line of tobamolite corresponds to a diffraction line observed near 7.7 ° (20). Figure 2 shows a schematic diagram of the calculation method.

[Sawability]

'' The hardened body was cut using a woodworking saw and evaluated based on the ease of cutting and the condition of the cut surface. Examples 1 to 13

In these examples, the following solid mixtures and water were used in the amounts shown in Table 1 as raw materials for the cured product. That is, as the siliceous raw material, ground silica powder (blane specific surface area: 11,100 cm Vg) and silica fume (EFACO, Egypt) were used. Further, as a cement, an early Portland cement was used in Examples 1 to 8, and a normal Portland cement was used in Examples 9 to 13. Quicklime (purity 98%) as calcareous raw material, its octahydrate as aluminum sulfate, gypsum dihydrate as other sulfate compound, surfactant In Examples 1 to 5, polyoxyethylene alkyl ether, a nonionic surfactant, was used. In Examples 6 to 13, Emal 20T, an anionic surfactant, was used (Kao, Japan). Co., Ltd.), methylcellulose as a viscosity modifier, alkyl-modified silicone (Shin-Etsu Chemical Co., Ltd., Japan) as a defoamer, and finely ground pulp as organic fibers (Examples 10 and 1). 3) was used. Here, aluminum sulfate 18 hydrate and gypsum dihydrate are shown in Table 1 by weight of their anhydrates. Further, the amount of the surfactant added was represented by weight% based on the solid content of the foaming agent. The water Z solid ratio shown in Table 1 is the weight ratio of water to the weight of the solid mixture.

In Examples 1 to 8, in a 15 L stainless steel tank charged with water heated to 50 ° C, ground silica powder, silica fume, quicklime, high-speed portland cement, and sulfuric acid were used. Aluminium octahydrate, gypsum, gypsum, a viscosity modifier and an antifoaming agent were first charged, and the stainless steel tank was heated to 50 ° C while a stirrer (Ultra stirrer DC—CHRM 25 The mixture was stirred and mixed under atmospheric pressure for 2 hours at a rotation speed of 1200 rpm (Japan, manufactured by Inuchi Seieido Co., Ltd.) while suppressing the evaporation of water. Next, only in Examples 4 and 5, the aqueous slurry was heated to 40 ° C, and then quicklime was secondly injected and stirred at 40 ° C for 1 minute. After all components of the solid mixture were mixed, aluminum powder to which a surfactant was added was added as a foaming agent, and the mixture was stirred for 20 seconds. The slurry was poured into a mold (30 cm × 30 cm × 20 cm) and foamed in the mold. Immediately after the aqueous slurry was poured into the mold, the temperature was maintained at 60 in a state where evaporation of water was prevented, and pre-cured. In Examples 9 to 13, ordinary Portland cement was used as the cement, and water was heated to 60 ° C, and the mixture was stirred while heating at 60 ° C. Other than the above, the procedure was the same as in Example 1. However, only in Example 13 quicklime was secondarily charged and stirred at 60 ° C for 1 minute.

Next, the pre-cured product is removed from the mold, cured at 190 ° C. for 4 hours under a high-temperature and high-pressure atmosphere in a saturated steam atmosphere in an autoclave, and then dried to obtain a molded product (calcium silicate cured). Body) was obtained.

Table 3 shows various physical properties of the obtained molded body. 1 and 2 show powder X-ray charts of the cured calcium silicate obtained in Example 13. Example 14

Using the raw materials shown in Table 1, molding was carried out in the same manner as in Example 9 except that no surfactant and antifoaming agent were used. Table 3 shows various physical properties of the obtained molded body. Example 15

Using the raw materials shown in Table 1, surfactants and defoamers Except for that, molding was performed in the same manner as in Example 11. Table 3 shows various physical properties of the obtained molded body. Comparative Examples 1 and 2

A molded product was obtained in the same manner as in Examples 4 and 13, except that the surfactant, the viscosity modifier and the defoamer were not added. Table 4 shows various physical properties of the obtained molded body. Comparative Example 3

Molding was performed in the same manner as in Comparative Example 2 using the raw materials shown in Table 2. Table 4 shows various physical properties of the obtained molded body. Comparative Examples 4 and 5

Molding was carried out in the same manner as in Example 13 except that no surfactant, antifoaming agent, and ground pulp were added. Table 4 shows various physical properties of the obtained molded body. Comparative Example 6

Molding was performed in the same manner as in Example 13 except that the surfactant and the antifoaming agent were not added. Table 4 shows various physical properties of the obtained molded body. Comparative Example 7 Using the raw materials shown in Table 2, molding was performed in the same manner as in Example 14 except that no viscosity modifier and aluminum powder were used. Table 4 shows various physical properties of the obtained molded body. Comparative Example 8

ALC for commercial insulation (HEBEL DAMMPLATTE: Germany

HEBEL) and various physical properties were measured. Table 4 shows the obtained results. Comparative Example 9

Silica with an average particle size of about 2 O ^ m 51 parts by weight, early-strength Portland cement 42 parts by weight, quicklime 5 parts by weight, gypsum dihydrate 2 parts by weight of solid content of 45 ° C 78 parts by weight of water, Emul 20 T as a surfactant (manufactured by Kao Corporation, Japan) 0.5 part by weight 0.4 part by weight of methylcellulose as a viscosity modifier and melamine-based 0.4 parts by weight of thickener, alkyl-modified silicone oil (made by Shin-Etsu Chemical Co., Ltd., Japan) as defoamer 0.4 parts by weight Metal aluminum powder as foaming agent 0.12 parts by weight The aqueous slurry was poured into a mold and cured at 45 ° C until it became a semi-cured state. The temperature of the aqueous slurry before pouring into the mold was 43 ° C. After that, the pre-cured product is removed from the mold, and the autoclave is heated and heated at 180 ° C and 10 atmospheres for 4 hours under saturated steam atmosphere. Lived. After drying, various physical properties were measured and are shown in Table 4. Comparative Example 10

A straight part sample of a commercially available ALC sound absorbing material (Shizuka Light; manufactured by Clion Corporation, Japan) was sampled and various physical properties were measured. Table 4 shows the obtained results. Comparative Example 1 1

A commercially available rock wool (Homemat; manufactured by Nichias Co., Ltd. in Japan) was collected and various physical properties were measured. Table 4 shows the results. Flexural strength and compressive strength could not be measured because the shape of the sample could not be maintained. In addition, the sawing property could not be evaluated because the fiber was pulled and could not be cut. Comparative Example 1 2

Commercially available glass wool (Mat Ace; manufactured by Asahi Fiber Glass Co., Ltd., home country) was collected and various physical properties were measured. Table 4 shows the obtained results. Flexural strength and compressive strength could not be measured because the shape of the sample could not be maintained. Sawability could not be evaluated because the fiber could not be cut because it was pulled Example Example Example Example Example Example

Raw material 1 2 3 4 5

Primary cement 1 2 3 .2 1 2 3 .2 1 2 3 .2 6 1 .8 6 1 .8 Quick lime primary dan 24.6 24 .6 24 .6 2 0 .9 2 0 .9 Quick lime secondary (Parts by weight) 0.0 0 .0.0 0 .0 48.8 .8 48.8 Aishite powder-powder (next cast) 60.0 .0 6 .0 6 .0 .0 6 .8 6 9.8 Primary Lithuary Part 40.0 4 0 .0 4 0 .0 4 6.5 .5 46.5 Gypsum Primary (parts by weight) 1 1 .7 1 1 .7 1 1 .7 1 1.7 1 1.7 Aluminum sulphate primary (parts by weight) 10.8 10.8 10.8 10.8 10.8 10.8 water (parts by weight) 8 7 8.5 5 8 7 8. 5 8 7 8 5 8 7 8 5 8 7 8.5 Pulverized pulp (parts by weight) 0.0 0 0 0 0 0 0 0 0 0 0 0

Aluminum powder (parts by weight) 1.1 9 1 .1 9 1 .1 9 1 .1 4 .1 .4 Surfactant (% by weight) 2 1 0 1 0 0 1 0 1 0 0

Viscosity modifier (parts by weight) 0.180.180.180.180.18 Defoamer 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

C a O / S i O ₂ (molar ratio) 0.93 0.93 0.93 0.93 0.93 0.93 water / solids ratio (weight ratio) 3.25.30.253. 2 5 3 .2 5 3 .2 5

C a 〇 Z cement 0 .2 0 .2 0 .2 1 .1 1 .1

Oxide conversion

1.2 1 1.2 1 1.2 1.2

(A 1 ₂ 0

Oxide conversion

(% By weight) 3.5 3.5 3.5 3.5 3.5 3.5

(S O

Four Table 1 (continued)

Example Example Example Example Example Example

material

6 7 8 9 1 0

Cement primary (parts by weight) 1 2 3 .2 1 2 3 .2 1 2 3 .2 1 2 7 .1 1 27.1 .1 Quick lime primary (parts by weight) 2 4 .6 2 4 .6 2 4. 6 2 5 .4 2 5 .4

Quicklime secondary (parts by weight) 0.00.00.00.00.00.00.00.0

Primary silica powder (parts by weight) 60.0.600.0.060.0.600.0.06.00 Primary silica fume primary (parts by weight) 40.0.040.040.04.0 0.0 40.0 0.0 Gypsum primary (parts by weight) 1 1.7 1 1.7 1 1 .7 110 .6 10.6 Primary aluminum sulfate (parts by weight) 1 0.8 1 0.81 0.8 1 1 .0 1 1 .0 Water (parts by weight) 8 7 8.5 .5 8 7 8 .5 8 7 8 .5 7 5 5 .6 7 5 5.6 Crushed pulp (parts by weight) 0.0 0.00.00.00.02.8 ^ aluminum powder (parts by weight) 1.19.111.91.19.111.51.15 Surfactant 4 4 0 1 0 0 0 100.10 Viscosity modifier (parts by weight) 0.180.180.180.150.15 Antifoamer (parts by weight) 0.280.280 . 2 8 0. 0 3 0. 0 3

C a 0 / S i 0 2 (molar ratio) 0.93 0.93 0.93 0.93 0.93 0.93 water Z solid ratio (weight ratio) 3.25.30.253. 2 5 2 .7 2.7 .7

CaO / cement 0.20 0.20 0.20 0.2

Oxide conversion

1.2 1 1.2 1 1.2 1.2

(A 1 ₂ O 3)

Oxide conversion

(Weight%) 3.5 3.5 3.5 3.5 3.2 3.2

(SO,)

Table 1 (continued)

Example Example Example Example Example Example Raw material

1 1 1 2 1 3 1 4 1 5 Cement primary (parts by weight) 1 2 7 .0 1 2 7 .0 5 3 .8 1 2 7 .1 1 2 7 .0 Quick lime primary (parts by weight) 2 5 4 2 5 .4 1 8 .3 2 5 .4 2 5 .4 Quick lime secondary (parts by weight) 0.0 0.04 0 2 .5 0 0 .0 Silica crushed powder primary (parts by weight) 6 0.060.0.060.0.060.0.06.00 Silicon fume primary (parts by weight) 40.0.400.0.040.040.040.00.0 Gypsum primary ( Parts by weight) 1 1 1 1 1 1 0 6 .0 1 0 .6 1 1 .1 aluminum sulphate primary (parts by weight) 2 3 .0 1 1 .1 0 .9 .4 1 1 .1 0. (Parts by weight) 100 8 10 8 9 9 9 6 4 2 .0 7 5 5 6 1 0 0 8. 2 2 Ground pulp (parts by weight) 0 .0 0 .0 7 .2 0 .0 0.0 Aluminum powder (parts by weight) 1.5 0.99. 0.91 0.95 1.1.5 3 3 Surfactant (% by weight) 0.10 0.10 0.10 0 Viscosity modifier (parts by weight) 0.210.20.13.0.150.20.2 Antifoaming agent (parts by weight) 0.030.0.0.030.0.0.0 0 0. 0 0

C a O / S i O 2 (molar ratio) 0.930.9.0.930.930.930.93 water / solid ratio (weight ratio) 3.5.4.02.7.72 7 3.5

C a O Z cement 0.2 0 .2 1 .1 0 .20.2 oxide equivalent

(Wt%) 2. 4 1. 2 1. 2 1. 2 2. 4 (A 1 2 O 3)

Oxide conversion

(Wt%) 4. 2 3. 2 3. 2 3. 2 4. 2 (S 0 3)

Table 2

Note: In Comparative Example 6, the aluminum powder was used in the form of an aluminum slurry. The concentration of aluminum powder in the aluminum slurry was 5% by weight based on the water used

Table 3

Example Example Example Example Example Example

1 2 3 4 5 Specific gravity (g / cm ³ ) 0.120.140.150.160.15 By powder X-ray diffraction

3.5 5 3 .3 3-4 4 .2 4 .1

I b / I a

X-ray powder diffraction

0. 3 2 0 .3 3 0 .3 3 0 .3 6 0 .3 5

I (0 0 2) / \ (2 2 0)

Bending strength (N / mm ² ) 0.13 0 .14 0 .15 0 .2 0 0 .2 1 4 4 0 .5 7 0 .5 7 00 Compressive strength (N / mm ² ) 0.3 10 .38 0 .Thermal conductivity (W / mK) 0 .04 8 0 .05 2 0 .0 5 3 0 .0 5 5 0 .0 5 4 Air permeability (mVh Pa) 6.1 ^{X 10 - 3 1. 3 X 10-} 2 1. 3 X 10 - 2 8. 3 X 10 - 3 8. 7 X 10_ 3 sawing of visually good good good good good

Table 3 (continued)

Example Example Example Example Example 6 7 8 9 10 Specific gravity (g / cm ³ ) 0.110.160.10.110.110.11 By powder X-ray diffraction

3.5 5 3 .3 3 .4 3 .7 3.7 Ib / Ia

X-ray powder diffraction

0. 3 3 0. 3 2 0. 3 3 0. 3 0 0. 3 1 I (0 0 2) / \ (2 2 0)

Bending strength (N / mm ² ) 0.15 0 .14 0 .16 0 .13 0 .15 Compressive strength (N / mm ² ) 0.38 0 .3 9 0.30. 27.30 Thermal conductivity (W / mK) 0.047 0 .55 0 .04 6 .0 4 .6 0 .0 4 5 Air permeability (mVh Pa) 3.8 X 10 ^{^{- 3 1. 1 X 10 - 2}} 9. 5X 10- 3 3. 4 X 10 - 3 2. 3 X 10 one ³ sawing can of visually good good good good good

Table 3 (continued)

Example Example Example Example Example Example Example

1 1 1 2 1 3 1 4 1 5 Specific gravity (g / cm ³ ) 0.083 0 .09 4 0.

4.03.3.4.3.03.7.4.1.

I b / I a

X-ray powder diffraction

0. 4 0 .0 .3 9 0 .3 4 0 .3 1 0 .3 2

I (0 0 2) / I (2 2 0)

Bending strength (N Roh ^{mm 2) 0. 0 7 4} 0. 0 8 1 0. 1 5 0. 1 4 0. 0 7 3

(N / mm ² ) 0.12 0 .14 0 .3 5 0 -2 8 0 .12 O Compressive strength Thermal conductivity (W / mK) 0.0 4 2 0 .0 4 3 0 .0 4 5 0.0 4 5 0.0 4 1 air permeability ^{(m 2 / h P a)} 5. 4X 10- 3 3. 3 X 10 one ³ 6. 5 X 10 one ⁴ 1. 8 X 1 0 one ³ 4. 0 X 10 one ³ sawing woody eye view good good good good good

Table 4

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6

P tray u Rika S / cm 0.1 1 0 1 1 j Π 1

Ri tree ± ■ A ■ $ IB OT i- ^

4.0 4.14-2 2 4.2.5 54.5 14.6

I b / I a powder X-ray diffraction

0.33 0.3 3 0.3 4 2 0.3 3 0.2 9 0.3 1 I (0 0 2) / I (2 2 0)

Bending strength (NZmm ² ) 0.15 0.14 0-1 3 0 .2 7 0 .5 2 0 .4 9 Compressive strength (N / mm ² ) 0.3 ² 0 .3 1 0 .2 3 0.75 1 .4 1 .3 9 Thermal conductivity (W / mK) 0.0 4 6 0 .0 4 6 0 .0 4 5 0 .0 5 4 0 .0 6 8 0 .0 7 0 Ventilation rate ^{(mVhPa) 3. 1 X 10- 5} 1. 1 X 10- 4 1. 9X 10- 5 9. 8X 10- 6 1. 8X 10- 6 2. 2X 10- 6 sawing of visually good good good good Good good

Table 4 (continued)

Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 1 0 Comparative Example 1 1 Comparative Example 1 2 Shiri υ-Π Π cr

U o o o p U π υ ο ϋ π u Π Γ \ 0 A Π U.

\ g / cm U powder X-ray diffraction

4.2.3.4.3.4.3.6 ― Ib / Ia powder X-ray diffraction

0.2 9 0 3 5 0 3 5 0 4 4 -... -.. 1 (0 0 2) / 1 (2 2 0) Bending strength (N / mm ²⁾ 1. 5 9 0 1 7 0 4 200.440 Compressive strength (N / mm ² ) 5.4.0.5 11.3 1.5 .5 0 Thermal conductivity (W / mK) 0.10 60.0 .04 43.0. 1 3 2 0.1 2 1 0.0 4 2 0.0 4 air permeability ^{(mVhPa) 1. 1X 10- 8 1.} 5X10- 4 9. 4X10-3 2. 1X10- 2 0. 1 3 0. 1 5 Sawability Visually good Good powder loss Good Good Cannot be cut Not cut

Industrial applicability

The hardened calcium silicate of the present invention is required to have not only light weight and high strength, but also nonflammability, and also have high heat insulation and high air permeability, and therefore have dynamic heat insulation. It can be used advantageously as a building wall material (dynamic insulation material) or sound absorbing material.

Whereas conventional dynamic insulation materials were not completely made of non-combustible materials, the cured calcium silicate of the present invention is non-combustible and can have the shape of a panel. Therefore, the construction is simple and the airtightness required for the dynamic insulation technology can be easily secured.

Claims

The scope of the claims

1. (1) The bending strength is more than 0.05MPa,

(2) Thermal conductivity is 0.02 ~ 0.1 l Wm- i K- ¹ , and

(3) permeability is ^{5 X 1 0 - 4 ~ 1} m 2 h - 1 shall apply in P a one ¹ below, calcium silicate hardened body showing the dynamic insulation properties.

2. The thermal conductivity is between 0.02 and 0.08 Wm! ! The cured product of claim 1, wherein the cured product is not more than ¹ .

3. The cured calcium silicate according to claim 1, wherein the thermal conductivity is 0.02 to 0.6 Wm- ¹ or less.

4. It consists mainly of tobermorite, and the diffraction peak intensity Ib of the (220) plane of tobermorite in powder X-ray diffraction is higher than that of (2220) and (22) planes of tobermorite. 2) A relationship of IbIa≥3 between the minimum value of the diffraction intensity Ia and the minimum value of the diffraction intensity Ia in the angle region between the two diffraction peaks of the surface. The cured product of calcium silicate according to item 1.

5. It is characterized by including the following steps (1) to (4) A method for producing a cured product of calcium silicate.

(1) To provide an aqueous slurry containing water and a solid mixture, wherein the solid mixture is substantially selected from the group consisting of siliceous raw materials, cement, aluminum sulfate and hydrates thereof. It consists of at least one aluminum compound, other sulphate compounds and, in some cases, calcareous raw materials.

The amount of the aqueous in Sula rie of the aluminum compound, the terms of oxide (A 1 ₂ 0 ₃₎ 0 by weight of the solid mixture. 0 9-1 0% by weight, and other sulfuric acid compound the amount of aqueous scan La Li one is, is rather also the aluminum sulfate including their hydrates, than zero. 1 5 to 1 5 wt% der relative to the weight of the solid mixture with S 0 ₃ weight basis ,

The weight ratio of the water to the solid mixture is 2.3 to 5.5;

The weight ratio of the calcareous raw material to the cement is 0.6 or less.

(2) Add a foaming agent to the aqueous slurry.

(3) Inject the aqueous slurry into a mold.

(4) After the aqueous slurry has been pre-cured, it is cured by autoclaving.

6. The foaming agent is at least one selected from the group consisting of aluminum powder and aluminum-containing aqueous slurry. 6. The method according to claim 5, wherein the foaming agent is used in an amount of from 0.03 to 0.95% by weight, based on the weight of the solid mixture, in terms of solids.

(1) Providing an aqueous slurry containing water and a solid mixture, wherein the solid mixture is substantially selected from the group consisting of siliceous raw materials, cement, aluminum sulfate and hydrates thereof At least one aluminium compound, other sulfate compounds, and possibly calcareous raw materials,

The amount of the aqueous in Sula rie of the aluminum compound, the terms of oxide (A 1 ₂ O ₃₎ 0 by weight of the solid mixture in. 0 9-1 0% by weight, and other sulfuric acid compound the amount of aqueous Sula Li one is, is rather also the aluminum sulfate including their hydrates, than zero. 1 5 to 1 5 wt% der relative to the weight of the solid mixture with S 〇 ₃ weight basis,

The weight ratio of the water to the solid mixture is 2.3 to 5.5;

The weight ratio of the calcareous raw material to the cement exceeds 0.6.

(2) Add a foaming agent to the aqueous slurry.

8. The foaming agent is at least one foaming agent selected from the group consisting of aluminum powder and an aluminum-containing aqueous slurry, and the foaming agent is converted to a solid in terms of solids. The method according to claim 7, characterized in that 0.03 to 0.95% by weight is used based on the weight of the mixture.

9. The surfactant is at least one compound selected from the group consisting of higher alcohol sulfates, higher alcohol sulfates, and polyoxyethylene alkyl ethers, The method according to claim 7 or 8, wherein the surfactant is used in an amount of 0.01 to 200% by weight based on the solid weight of the foaming agent.

10. The viscosity modifier is at least one compound selected from the group consisting of methylcellulose and polyvinyl alcohol. The method according to any one of claims 7 to 9, wherein the viscosity modifier is used in an amount of 0.01 to 1% by weight based on the weight of the solid mixture.

11. The antifoaming agent is at least one compound selected from the group consisting of silicones, fatty acids, fatty acid esters, alcohols, and phosphoric esters, wherein the antifoaming agent is The method according to any of claims 7 to 10, characterized in that 0.001 to 3% by weight based on the weight of the solid mixture is used.