JP5080077B2 - INORGANIC MOLDED BODY AND PROCESS FOR PRODUCING THE SAME - Google Patents

Description

  The present invention relates to an inorganic molded body mainly composed of a hydraulic inorganic material, a siliceous material, and a wood reinforcing material, and a method for producing the same.

Conventionally, a suitable amount of water and extrusion aid (thickening agent) are added and mixed with cement and other hydraulic inorganic materials, siliceous-containing materials, and wood reinforcing materials as the main raw materials, and the raw material mixture is used in an extruder. There is a method for producing an inorganic molded body by so-called extrusion molding.
As the wood reinforcing material, pulp-based reinforcing fibers, polypropylene fibers, and organic fibers such as vinylon fibers are often used to maintain the strength after molding.
For example, Japanese Patent Application Laid-Open No. 2001-233653 discloses that specific pulp fibers and specific organic fibers are used.
However, organic fibers such as polypropylene fibers are expensive and thus increase the product price, making it difficult to provide products at low cost.
Moreover, wood powder may be used for the shape retention after extrusion molding.
For example, Japanese Patent Laid-Open No. 3-257052 discloses that glass fibers are used as reinforcing fibers and wood flour is added.
Japanese Patent Laid-Open No. 6-032643 discloses that vinylon fiber is used as the reinforcing fiber and that water repellent treated wood flour is added.
However, since expensive glass fibers and vinylon fibers are used as reinforcing fibers, it is difficult to provide products at low cost.
JP 2001-233653 A Japanese Patent Laid-Open No. 3-257052 JP-A-6-032643

  The present invention is to provide an inorganic molded article having good physical properties such as workability and inexpensive and a method for producing the same.

In order to solve the above-described problems, the inorganic molded body according to claim 1 includes a cement-based material that is a hydraulic inorganic material, a fine siliceous-containing material that is a siliceous-containing material, and a coarse siliceous material. It is obtained from a raw material mixture containing a containing material and wood flour and pulp as a wood reinforcing material.

  The inorganic molded body according to claim 2 is the inorganic molded body according to claim 1, wherein the cementitious material is 25 to 45 mass% with respect to the total solid content, and the siliceous-containing material. Is 25 to 45 mass%, and the wood reinforcing material is 7 to 15 mass%.

Further, the inorganic molded product according to claim 1, based on the entire solid content of the siliceous-containing material, the pulverized siliceous containing material is 20 to 50 wt%, the total solids of the wood reinforcement It is characterized in that the wood flour is 10 to 60% by mass with respect to minutes.

Further, the inorganic molded product according to claim 1, wherein the finely divided siliceous containing material is a Blaine specific surface area 7000~11000cm ² / g, the coarse powder siliceous containing material, Blaine specific surface area 3000~4000cm ² / g.

In addition, the inorganic molded body according to claim 3 is the inorganic molded body according to claim 1 or 2 , wherein the wood powder is a portion passing through a standard sieve 16 mesh, and the pulp has an average fiber length of 0. .3 to 1.5 mm.

The inorganic molded body according to claim 4 is characterized in that the inorganic molded body according to claim 1 or 3 further contains a thickener and a water reducing agent.

The method for producing an inorganic molded body according to claim 5 includes a cement-based material, a fine siliceous-containing material and a coarse siliceous-containing material that are siliceous-containing materials, and a wood that is a wood reinforcing material. Curing and curing the intermediate product extruded in the step of kneading a raw material containing powder and pulp and an appropriate amount of water to form a raw material mixture, the step of extruding the raw material mixture, and the step of extruding As a siliceous material, use one or more of siliceous material, siliceous powder, diatomaceous earth, silica fume, fly ash, bottom ash, blast furnace slag, steel slag, and shirasu balloon. With respect to the total solid content, the fine silicic acid-containing material is 20 to 50% by mass, and with respect to the total solid content of the wood reinforcing material, the wood powder is 10 to 60% by mass. Brain ratio Using those areas 7000~11000cm ² / g, as coarse siliceous containing material, characterized in that it uses those Blaine specific surface area 3000~4000cm ² / g.

  ADVANTAGE OF THE INVENTION According to this invention, physical properties, such as workability, are favorable, and also an inexpensive inorganic molded object and its manufacturing method can be provided.

Hereinafter, the best mode for carrying out the present invention will be described.
The inorganic molded body of the present invention is mainly composed of a hydraulic inorganic material, a siliceous material, and a wood reinforcing material.

[Hydraulic inorganic material]
The hydraulic inorganic material is a material that begins to harden when it comes into contact with water, such as cement and lime.
As the hydraulic inorganic material used in the present invention, cement-based materials such as Portland cement, silica cement, fly ash cement, and alumina cement are preferable.
Among them, it is preferable to use ordinary Portland cement.

[Silica-containing material]
The siliceous-containing material is a material containing silicic acid (SiO ₂ ) as a chemical composition, and includes siliceous sand and diatomaceous earth.
The siliceous-containing material used in the present invention, silica sand, silica flour, diatomaceous earth, silica fume, fly ash, bottom ash, blast furnace slag, steel slag, there is Shirasu balloons.
In particular, it is preferable to use silica sand or fly ash.

[Coarse powdered siliceous material]
As the coarse siliceous material used in the present invention, it is preferable to use a material having a specific surface area of 3000 to 4000 cm ² / g among the siliceous materials.
If the Blaine specific surface area is rougher than 3000 cm ² / g, the reactivity of the calcium silicate reaction becomes low.

[Fine powdered siliceous material]
As the finely divided siliceous material used in the present invention, it is preferable to use a material having a Blaine specific surface area of 7000 to 11000 cm ² / g from the siliceous material.
Moreover, you may use what grind | pulverized the said coarse siliceous-containing material with the ball mill or the roller mill, and was pulverized to the said Blaine specific surface area.
Even if the Blaine specific surface area is finer than 11000 cm ² / g, it does not contribute much to the improvement of physical properties, and conversely, it becomes difficult to handle as a powder, leading to an increase in cost.

[Wood reinforcement]
Examples of the wood reinforcing material include wood powder, wood fragments, wood wool, wood fiber, pulp, wood fiber bundle, wood fiber, etc. As the wood reinforcing material used in the present invention, a combination of wood powder and pulp is preferable. .
Furthermore, as wood flour, what is a standard sieve 16 mesh passage part is preferable, and it is more preferable to use the standard sieve 30 mesh passage part.
The pulp preferably has an average fiber length of 0.3 to 1.5 mm (according to the JAPAN TAPPI paper pulp test method).
As the wood species of wood flour to be used, cedar and cedar that contain a large amount of curing inhibitory components can be selected as well as cypress and beech, which do not contain much curing inhibitory components.
Moreover, as a tree species of the pulp to be used, LUKP and LBKP are preferable.

[Thickener]
The thickener used in the present invention is used as an extrusion aid. By increasing the viscosity, the extrusion pressure is reduced and the formability is improved.
Specific examples include cellulose derivatives such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, and hydroxymethyl cellulose, and PVA. It is preferable to use a cellulose derivative.

[Water reducing agent]
As the water reducing agent used in the present invention, it is preferable to use a carboxylic acid type, a sulfonic acid type or a polyethylene glycol type.
As the carboxylic acid-based compounds, modified polycarboxylic acids such as ether-modified products and ester-modified products of polymethacrylic acid, oxycarboxylic acids, and the like are used.
Examples of sulfonic acid-based compounds include naphthalene sulfonic acid, lignin sulfonic acid, alkylallyl sulfonic acid, and melamine sulfonic acid, and it is particularly preferable to use a naphthalene sulfonic acid / formalin condensate salt.

[Others]
In addition, an inorganic lightweight body, an organic lightweight body, a waste material of an inorganic molded body, a ground product of an intermediate product, and the like may be added as appropriate.
For example, mica usually has a layered structure, is not hygroscopic, and is a highly elastic body having rigidity, which contributes to dimensional stability of the product.
As the mica used in the present invention, flakes having an average particle diameter of 200 μm to 700 μm and an aspect ratio of 60 to 100 are preferable.
In addition, the aspect ratio in this case means the ratio of thickness to particle diameter.
A pigment may be added.
Examples of pigments include titanium oxide, lead white (basic lead carbonate), zinc white (zinc oxide), antimony trioxide, carbon black, yellow lead (lead chromate), yellow iron oxide (hydrous ferric hydroxide), and red pepper (Ferric oxide), cadmium pigment, cobalt pigment, copper pigment, calcium carbonate, barium sulfate, alumina white, silica powder, clay and the like.

[Raw material formulation]
Next, the raw material mixing ratio of the inorganic molded body according to the present invention will be described.
In this invention, it mixes with 25-45 mass% of hydraulic inorganic materials, 25-45 mass% of siliceous containing materials, and 7-15 mass% of wood reinforcement materials, and let it be a raw material mixture.
When the amount of the hydraulic inorganic material is more than 45% by mass, there is a risk that the long-term durability of the final molded body is lowered. When the amount is less than 25% by mass, the hydraulic component is small and the curing is insufficient, and the bending strength is low. There is a risk of problems in various physical properties.
When the siliceous material content is more than 45% by mass, there are many silicic acid components that do not react in the calcium silicate reaction, and there is a possibility that various physical properties such as freeze-thaw resistance may occur. If the amount is too small, there is a risk that the amount of silicic acid required for the calcium silicate reaction is small and the bending strength is lowered.
If the amount of the wood reinforcing material is more than 15% by mass, the fluidity tends to deteriorate and the production becomes difficult, and if it is less than 7% by mass, there may be a problem in physical properties such as bending strength.
In addition, the fine siliceous-containing material is 20 to 50% by mass with respect to the total siliceous-containing material, and the wooden powder is mixed to be 10 to 60% by mass with respect to the whole wooden reinforcing material. is there.
If the amount of fine siliceous material is more than 50% by mass relative to the total siliceous material, the product becomes too hard and the workability deteriorates, and if it is less than 20% by mass, it does not contribute to the final strength. .
When the amount of wood powder is more than 60% by mass with respect to the whole wood reinforcing material, the amount of deflection is reduced and the toughness is lost, and when it is less than 10% by mass, it does not contribute to shape retention. There is no cost merit.
The mass ratio between the hydraulic inorganic material and the siliceous material is preferably 40:60 to 60:40.
If the mass ratio of the siliceous material is lower than 40%, there is a risk that the calcium silicate reaction will not occur sufficiently, and if it exceeds 60%, there are many silicic acids that do not react in the calcium silicate reaction. Will do.

[Production method]
Next, the manufacturing method of the inorganic molded object which concerns on this invention is demonstrated.
First, a raw material obtained by kneading an appropriate amount of water with a cement-based material, a fine siliceous material, a coarse siliceous material, wood powder, wood pulp, and a thickener with a kneader etc. Mix.
Here, a water reducing agent may be added to reduce the amount of water added.
Next, the raw material mixture is extruded using an extruder.
Then, the extruded molded intermediate is cured and cured to become an inorganic molded body.
Curing is preferably carried out at 40 to 80 ° C. for 6 to 12 hours, and curing is carried out in an autoclave at 145 to 170 ° C. for 6 to 10 hours.
Thus, an inorganic molded body is manufactured, and the inorganic molded body is used as an outer wall material or the like.

Examples of the present invention will be given below.
Examples 1-6 and Comparative Examples 1-4 were manufactured with the raw material composition shown in Tables 1 and 2.
Ordinary Portland cement as cement, coarse powder as siliceous containing material Blaine specific surface area of 3700 cm 2 / ^g sand and fly ash, silica sand of Blaine specific surface area of 10000 cm 2 / ^g as fine siliceous containing material, as wood reinforcement , Wood grain of standard sieve 16 mesh (opening 1mm), average fiber length 1.0mm
Pulp, expanded polystyrene beads as a lightweight body, hydroxyethyl methylcellulose as a thickener (trade name Metroze manufactured by Shin-Etsu Chemical Co., Ltd.), naphthalenesulfonic acid / formalin condensate salt as a water reducing agent (trade name manufactured by Kao Corporation) Mighty).
Curing was performed at 60 ° C. for 10 hours, and curing was performed in an autoclave at 165 ° C. for 8 hours.
Various physical properties are shown in Tables 3 and 4.
The bending strength and the maximum deflection were measured according to JIS A 1408.
Extrusion stability is comprehensively judged by visual inspection whether the speed, direction, flow, thickness, width, etc. of the extruded product at the time of extrusion molding is stable, very good → ◎, good → ○, somewhat bad → △, bad → ×, evaluated.
The surface property was evaluated by visually judging whether or not there was unevenness or cracks on the surface of the extruded product immediately after extrusion, and evaluated as very good → ◎, good → ○, slightly bad → Δ, and bad → ×.
The workability is judged by the suitability of nailing as a product after curing and curing the extruded product,
It was evaluated as very good → ◎, good → ○, slightly bad → △, bad → ×.
Formability is judged by cutting sharpness, fluffing, chipping, etc. at the time of cutting with a cutter of the molded body after curing and curing the extruded molded body, very good → ◎, good → ○, somewhat bad → △, Evaluated as bad → ×.

  According to Table 3, wood dust and pulp are added as the wood reinforcing material, and the wood dust is about 45% by mass between 10 to 60% by mass with respect to the whole wood reinforcing material, and further the fine silicic acid-containing material And coarse silicate-containing material is added, and the fine silicate-containing material is about 23% by mass between 20-50% by mass with respect to the total siliceous-containing material. The evaluation was ○ (good), the surface property was ○ (good), the workability was ○ (good), and the formability was ○ to Δ (good to slightly bad).

Wood powder and pulp are added as a wood reinforcing material, and the wood powder is about 23% by mass between 10 to 60% by mass with respect to the whole wood reinforcing material. In Example 2, in which the fine siliceous-containing material is about 23% by mass between 20 to 50% by mass with respect to the total siliceous-containing material, the extrusion stability is 0 to Δ ( Evaluation of good to slightly bad), surface property is also evaluated as ○ to △ (good to slightly bad), workability is ◎ to ○ (very good to good), and formability is evaluated as ○ to △ (good to slightly bad). Met.

Wood powder and pulp are added as a wood reinforcing material, and the wood powder is about 20% by mass between 10 to 60% by mass with respect to the whole wood reinforcing material, and further, a fine siliceous material and a coarse siliceous material. In Example 3, the content of finely divided siliceous material is about 24% by mass between 20 to 50% by mass with respect to the total siliceous material, and the extrusion stability is good (good). In the evaluation, the surface property was evaluated as ◎ (very good), the workability was evaluated as ◯ (good), and the formability was evaluated as ◯ (good).

Wood powder and pulp are added as the wood reinforcing material, and the wood powder is about 38% by mass between 10 to 60% by mass with respect to the whole wood reinforcing material. Further, the fine siliceous material and the coarse silicic acid are included. In Example 4, in which the fine siliceous-containing material is about 23% by mass between 20 to 50% by mass with respect to the total siliceous-containing material, the extrusion stability is good (good) In the evaluation, the surface property was ○ (good), the workability was ◎ to ○ (very good to good), and the formability was ○ to △ (good to somewhat bad).

Wood powder and pulp are added as the wood reinforcing material, and the wood powder is about 38% by mass between 10 to 60% by mass with respect to the whole wood reinforcing material. Further, the fine siliceous material and the coarse silicic acid are included. In Example 5 in which the fine silicic acid-containing material is about 49% by mass between 20 to 50% by mass with respect to the total silicic acid-containing material, the extrusion stability is In the evaluation of (very good to good), the surface property was ○ (good), the workability was ○ to Δ (good to slightly bad), and the moldability was ○ (good).

Wood powder and pulp are added as the wood reinforcing material, and the wood powder is about 38% by mass between 10 to 60% by mass with respect to the whole wood reinforcing material. Further, the fine siliceous material and the coarse silicic acid are included. In Example 6, in which the fine siliceous-containing material is about 20% by mass between 20 to 50% by mass with respect to the total siliceous-containing material, the extrusion stability is good (good) In the evaluation, the surface property was also evaluated as ◯ (good), the workability was evaluated as ◯ (good), and the formability was evaluated as ◯ to Δ (good to slightly bad).

About Examples 1-6, even if it does not use expensive reinforcement fibers, such as a polypropylene fiber, various physical properties equivalent to the used comparative example 1 can be obtained, and also it can manufacture an inorganic fabrication object cheaply. did it.

  According to Table 4, Comparative Example 1 in which only pulp was added as a wood reinforcing material and 2% by mass of polypropylene fiber was added was used as a blank. Extrusion stability was evaluated as ○ to △ (good to slightly bad), surface property was evaluated as ○ (good), workability was evaluated as ○ to △ (good to slightly bad), and formability was evaluated as ○ (good). Compared to 1, Examples 1 to 6 show inferior values.

In Comparative Example 2 in which only wood powder is added as a wood reinforcing material, the extrusion stability is evaluated as x (poor), the surface property is Δ (slightly bad), and the workability is Δ to x (slightly bad to bad). The formability was evaluated as x (bad).

In Comparative Example 3 in which only 13% by mass of pulp was added as a wood reinforcing material, the extrusion stability was evaluated as ◯ to △ (good to slightly bad), but the surface property was △ (slightly bad) and workability. The evaluation was ○ to Δ (good to slightly bad), and the formability was evaluated to be x (bad).

Comparison where finely divided siliceous-containing material and coarsely divided siliceous-containing material are added, and the total fine siliceous-containing material is about 86% by mass, not between 20-50% by mass of finely divided siliceous-containing material In Example 4, the extrusion stability was ◎ to 〜 (very good to good), the surface property was ◯ (good), and the formability was 性 (very good), but the workability was △ to 性The evaluation was x (slightly bad to bad).

Furthermore, Examples 7 to 9 and Comparative Examples 5 to 6 were produced with the raw material blends shown in Tables 5 and 6.
As a lightweight body, it manufactured on the raw material and hardening curing conditions similar to Examples 1-6 and Comparative Examples 1-4 except having used perlite instead of the expanded polystyrene bead.
Various physical properties are shown in Tables 7 and 8.
The measuring method and apparatus are the same as those in Examples 1 to 6 and Comparative Examples 1 to 4.

Wood powder and pulp are added as the wood reinforcing material, and the wood powder is about 38% by mass between 10 to 60% by mass with respect to the whole wood reinforcing material. Further, the fine siliceous material and the coarse silicic acid are included. Example 7 in which about 20% by mass of the fine siliceous-containing material is between 20 and 50% by mass with respect to the total siliceous-containing material is added. In the evaluation (good to slightly bad), the surface property was ○ (good), the workability was ◎ to ○ (very good to good), and the formability was ○ to △ (good to slightly bad).

Wood powder and pulp are added as a wood reinforcing material, and the wood powder is about 20% by mass between 10 to 60% by mass with respect to the whole wood reinforcing material, and further, a fine siliceous material and a coarse siliceous material. In Example 8, in which the fine silicic acid-containing material is about 22% by mass between 20 to 50% by mass with respect to the total silicic acid-containing material, the extrusion stability is 0 to Δ ( The evaluation was good (slightly bad), the surface property was ○ (good), the workability was good (good), and the formability was good (good).

Wood powder and pulp are added as the wood reinforcing material, and the wood powder is about 50% by mass between 10 to 60% by mass with respect to the whole wood reinforcing material, and further the fine silicic acid-containing material and coarse silicic acid Example 9 in which the content of fine siliceous material is about 22% by mass between 20 and 50% by mass with respect to the total silicic acid-containing material, The evaluation was good (slightly bad), the surface property was ○ (good), the workability was good (good), and the formability was good (good).

In Comparative Example 5 in which only wood powder is added as a wood reinforcing material, the extrusion stability is evaluated as Δ to × (somewhat bad to bad), the surface property is Δ (somewhat bad), and the workability is Δ to × ( Slightly bad to bad), the formability was evaluated as △ (somewhat bad).

Comparative Example 6 in which only the pulp was added as the wood reinforcing material was evaluated as having an extrusion stability of ◯ to △ (good to slightly bad) and a workability of ◯ to △ (good to slightly bad). The evaluation was x (bad), and the formability was x (bad).

Claims (5)

From a raw material mixture containing a cement-based material that is a hydraulic inorganic material, a fine silicic acid-containing material that is a siliceous material, and a coarse silicic acid-containing material, and wood flour and pulp that are wood reinforcing materials Obtained,
The siliceous material is one or more of silica sand, silica powder, diatomaceous earth, silica fume, fly ash, bottom ash, blast furnace slag, steel slag, shirasu balloon,
Based on the total solid content of the siliceous material, the fine siliceous material is 20 to 50% by mass,
The wood powder is 10 to 60% by mass with respect to the total solid content of the wood reinforcing material,
The fine siliceous-containing material has a Blaine specific surface area of 7000 to 11000 cm ² / g,
An inorganic molded body characterized in that the coarse powder siliceous material has a Blaine specific surface area of 3000 to 4000 cm ² / g. The cementitious material is 25 to 45% by mass, the siliceous material is 25 to 45% by mass, and the wood reinforcing material is 7 to 15% by mass with respect to the total solid content. The inorganic molded body according to claim 1. 3. The inorganic molded body according to claim 1, wherein the wood powder is a portion passing through a standard sieve of 16 mesh, and the pulp has an average fiber length of 0.3 to 1.5 mm. Furthermore, the thickening agent and the water reducing agent are contained, The inorganic molded object of Claim 1 or Claim 3 characterized by the above-mentioned. A raw material containing a cement-based material, a fine silicate-containing material and a coarse silicate-containing material as a siliceous-containing material, a wood flour and pulp as a wood reinforcing material, and an appropriate amount of water are kneaded. A raw material mixture, a step of extruding the raw material mixture, and a step of curing and curing the molding intermediate extruded in the extruding step,
As siliceous material, use one or more of silica sand, silica powder, diatomaceous earth, silica fume, fly ash, bottom ash, blast furnace slag, steel slag, shirasu balloon,
With respect to the total solid content of the siliceous material, the fine siliceous material is 20 to 50% by mass,
With respect to the total solid content of the wood reinforcing material, the wood powder is 10 to 60% by mass,
As the fine siliceous material, a material having a Blaine specific surface area of 7000 to 11000 cm ² / g is used,
A method for producing an inorganic molded body, wherein a coarse powder siliceous material having a specific surface area of 3000 to 4000 cm ² / g is used.