JPH0549620B2 - - Google Patents

Description

[Detailed description of the invention]

"Object of the invention" The present invention relates to a method for manufacturing a hydraulic inorganic member,
The present invention aims to provide a method for manufacturing a hydraulic inorganic member having excellent strength characteristics, such as Portland cement, simply and at low cost. Industrial application field Manufacturing technology for hydraulic inorganic materials such as cement and gypsum. Conventional technology It has been common practice to manufacture inorganic materials using Portland cement, gypsum, etc., and in this case, sand, gravel, and other aggregates are mixed and produced to produce materials for civil engineering or construction. It is also well known that it can be used as a member. Note that range concrete that uses resin instead of the above-mentioned Portland cement has also been known. Furthermore, in JP-A No. 52-53917, a plastic mixture consisting of gypsum hemihydrate, a water reducing agent, fibers such as asbestos, a thermosetting resin such as melamine resin, and water, that is, gypsum hemihydrate, using a water reducing agent. A mixture of dispersed gypsum hemihydrate is poured into a pressure mold, pressurized just before the gypsum hemihydrate starts setting, excess water and air is removed, and the mold is formed into a dense structure. After hardening, it is further heated. It is proposed that. Problems to be Solved by the Invention When using hydraulic biomaterial powders such as cement, in addition to the conventional and common products as described above, the amount of cement, etc. to be blended depends on the actual product obtained. Controls strength properties. That is, in order to increase the strength, it is essential to mix a large amount of cement, etc., which is expensive and has a limit. As mentioned above, range concrete requires a large amount of resin, making it expensive, and there is a limit to how high its strength can be made. Furthermore, since the binder is an organic resin, it has no fire resistance and cannot be used as an inorganic material. In the case of JP-A No. 52-53917 mentioned above, the type of water reducing agent is important, and even if the types of water reducing agents are mixed, the transverse rupture strength will be halved with double the amount of water reducing agent. As disclosed in the official gazette, the use of such a water reducing agent is naturally expensive, and the manufacturing operation is complicated and requires a large number of man-hours, which also makes it expensive. . Moreover, in cases where the molecular weight is less than 8,000 or more than 200,000 even if it is a simple melamine resin or a sulfonated melamine resin as described in JP-A-52-53917, it is necessary to improve the bending strength and compressive strength. I don't get it. "Structure of the Invention" Means for Solving the Problems When adding and kneading Portland cement or other hydraulic inorganic powder or the hydraulic inorganic powder with aggregate or other compounding materials, the molecular weight is 8,000 to 200,000.
1. A method for producing a hydraulic inorganic member, which comprises adding and mixing a sulfonated melamine resin, molding the product, and then heat-treating the product at room temperature or above. Effect A kneaded product using hydraulic inorganic powder with a molecular weight of 8000
By heat-treating the molded product by mixing sulfonated melamine resin of ~200,000, it is polymerized even in an alkaline system, and sufficiently high strength can be achieved. By appropriately using a catalyst, the above polymerization can be achieved even under temperature conditions close to room temperature. EXAMPLES To further explain the present invention as described above, in the present invention, as described above, when obtaining a kneaded molded product using Portland cement or the like, a sulfonated melamine resin is blended into the kneaded product, kneaded, and molded, Next, it is subjected to heat treatment. The heating temperature is generally 40 to 180°C, but examples of catalysts include organic sulfonic acids such as naphthalene sulfonic acid, dodecylbenzenesulfonic acid, and para-toluene sulfonic acid, their amine salts, and phosphoric acid. butanol ester,
The reaction can be accelerated by adding one or more of butanol ester of tetrachlorphthalic acid and inorganic salts, and polymerization can be appropriately achieved by heat treatment at room temperature or higher. As for the amount of the sulfonated melamine resin added, in general, bending strength can be improved even at around 0.8%, and in particular, a preferable increase in strength is obtained when it is 1% or more, and the compressive strength is also the same, but industrial The preferable range is 3% or more. Regarding the upper limit, even if it is added in excess of 30%, it cannot be expected that the bending or compressive strength will increase commensurate with the increase in the amount of resin. The molecular weight of such sulfonated melamine resin is 8,000 to 200,000, preferably 10,000 to 150,000, and the sulfonated melamine resin having a molecular weight in this range has an excellent dispersion effect on cement and other hydraulic inorganic materials. In addition, in the kneaded molded product, the polymer is formed by ionic bonding between divalent cations such as calcium in a hydraulic inorganic material such as cement and sulfonic acid in the resin, and the structure of the molded product becomes denser. It will be done. When the molecular weight is less than 8,000, it is difficult to achieve high strength appropriately, and when it exceeds 200,000, the miscibility with cement and other hydraulic inorganic substances becomes poor, making dispersion and kneading difficult. The products according to the present invention include water-soluble melamine resins such as methylol melamine, methyl etherified melamine, and their variations, aggregates that do not deteriorate at temperatures of about 200°C, anionic surfactants, and acrylic emulsions. A polymer resin and/or a catalyst such as naphthalene sulfonic acid may be used in combination. A specific manufacturing example of the product according to the present invention will be described below. Manufacturing example 1 1.5 parts of carbon fiber in 100 parts of ordinary Portland cement
1 part and 5 parts of polyacrylamide gel were added, and sulfonated melamine resin with a molecular weight of 20,000 was added and mixed in various amounts in the range of 0 to 35% of the cement weight (C), and the water-cement ratio (W/C) was mixed. 12
%, 18%, and 22% were mixed and molded, and then subjected to high-pressure steam heat treatment at 150°C for 180 minutes.The bending strength measurement results are as shown in Table 1, and the compressive strength The measurement results are shown in Table 2 below.

【table】

[Table] Production Example 2 Regarding the bending strength and compressive strength of a molded article made of a paste with a W/C of 22% that was mixed and adjusted in the same manner as Production Example 1 except that 5.0 parts of polyacrylamide gel was not blended. is the third
It is as shown in the table.

【table】

[Table] Production example 3 100 parts of ordinary Portland cement, 100 parts of river sand,
To a mixture of 100 parts of fine slag and 1.5 parts of acrylic emulsion, sulfonated melamine resin with a molecular weight of 40,000 was added in various amounts in the range of 0 to 35.0% based on the cement weight, as in Production Example 1,
Also, the water-cement ratio (W/C) is 30% and 35%.
The results of measuring the bending strength of each molded mortar prepared by kneading are shown in Table 4 below, and the results of measuring the compressive strength of each mortar are shown in Table 5 below. The bending strength is sufficiently improved at 0.8%, but almost no improvement is observed even when it is added in excess of 20%. Similarly, the compressive strength
A significant improvement is achieved by increasing the content from 0.5% to 0.8%, but even if it exceeds 30%, there is no improvement commensurate with the increase in the amount of sulfonated melamine resin.

【table】

【table】

[Table] Production Example 4 The composition was exactly the same as Production Example 3 except that 1.5 parts of acrylic emulsion was not used, and the water-cement ratio (W/C) was 30%, 35%, 40% and 50%. The bending strength of various kneaded products prepared, molded, and heat-treated with high-pressure steam at 150°C for 180 minutes is shown in Table 6, and the compressive strength is shown in Table 7 below. That's right. In other words, the bending strength of sulfonated melamine resin is
Although there is a significant improvement from 0.5% to 0.8%, it is the same as Production Example 3 that even if it exceeds 20%, it does not improve much, and the compressive strength also increases by 20%.
Even if the amount is added above, it can be said that it remains almost flat.

【table】

【table】

[Table] However, with respect to Production Example 4, except that the sulfonated melamine was changed to the resin shown in Table 8 below (the sulfonated melamine had a different molecular weight), etc. Example 4
Water cement (W/C) with exactly the same composition as that of
30%, 40% for W/C, 30%, 35%, 40% and 50 for methylolated melamine resin.
% various mixtures were prepared as Comparative Examples 1 to 4. In addition, for Production Example 4, only the heating conditions were
A mixture prepared at 40° C. for 5 hours was prepared as Comparative Example 5.

[Table] The kneaded products of Comparative Examples 1 to 4 were molded and then subjected to high-pressure steam heat treatment at 150°C for 180 minutes, and those of Comparative Example 5 were steam-cured at 40°C for 300 minutes only under the heating conditions of Production Example 4. The bending strength is as shown in Table 9 below, and the compressive strength is as shown in Table 10. Comparing with the results in Tables 6 and 7 above, Comparative Example 1
-4, the effect of using the sulfonated melamine resin according to the present invention is clearly shown by adding 0.8% or more, and by adding 7 to 20%, the bending strength is at least 50 Kg/cm ² or more, and the compressive strength is It was confirmed that the weight had improved by around 250Kg/ ^cm2 or even more, and we knew that we were achieving outstanding improvement results. In addition, in Comparative Example 5, in which the heat treatment conditions of Production Example 4 were changed to 40°C for 300 minutes, the improvement effect as in Production Example 4, which was subjected to high-temperature heat treatment, was not observed, but Comparative Examples 1 to
Compared to 4, it was confirmed that the bending strength was improved by at least 20 kg/cm ² or more and the compressive strength was improved by around 150 kg/cm ² or more by adding 7 to 20%, and the improvement effect was achieved. I learned.

【table】

[Table] Production Example 5 A sulfonated melamine resin having a molecular weight of 800,000 was mixed in a range of 0 to 35% to concrete according to the formulation (Kg/m ³ ) shown in Table 11 below.

[Table] Table 12 shows the results of measuring the bending strength of each of the concrete molded bodies obtained, and the following summarizes the results of measuring the compressive strength. There are 13 tables.

【table】

[Table] Production example 6 100 parts of ordinary Portland cement, 5 parts of polyacrylamide gel, and equal amounts of sulfonated melamine resin and methylol melamine resin with a molecular weight of 60,000 were mixed, and the resin content was varied in the range of 0 to 35%. At the same time, 1.5 parts of carbon fiber was added and mixed only in those with a W/C of 22%, and the paste was molded with the water-cement ratio adjusted to 12%, 18%, and 22%, and then molded at 150°C x 180°C. The bending strength of those subjected to high pressure steam heat treatment for 15 minutes is 14th.
The measurement results of compressive strength are as shown in the table below.
As shown in Table 15. That is, the bending strength is significantly improved when the content exceeds 0.5%, but the improvement is small even when the content exceeds 20%, especially 30%, and the same tendency is observed for the compressive strength.

【table】

[Table] Production Example 7 The same formulation as in Production Example 6 except that 5 parts of polyacrylamide gel was not used, and W/C was 22%.
The bending strength and compressive strength of the molded product made from the paste are as shown in Table 16 below.

[Table] Production example 8 100 parts of ordinary Portland cement, 100 parts of river sand,
100 parts of granulated blast furnace slag, 1.5 parts of acrylic emulsion
A mixture of sulfonated melamine resin and methylol melamine resin with a molecular weight of 100,000 in an equal weight ratio was added to the mixture in various amounts in the range of 0 to 35.0%, and the water-cement ratio (W/
The results of measuring the bending strength of mortar prepared by mixing and adjusting C) at 30% and 35% are shown in Table 17 below, and the results of measuring the compressive strength are shown below. As shown in Table 18, the bending strength increases significantly when the amount of sulfonated melamine resin added exceeds 0.5%.
Sufficient improvement is achieved when it is added at 1.0% or more, but almost no improvement is observed when it is added in excess of 30%. Similarly, the compressive strength is significantly improved by changing from 0.5% to 1.0%, but even if it exceeds 20%, especially 30%, there is no improvement commensurate with the increase in the amount of melamine resin. .

【table】

[Table] Production Example 9 The composition was exactly the same as Production Example 8 except that 1.5 parts of acrylic emulsion was not used, and the water-cement ratio (W/C) was 35%, 40%, and 50%. After preparing the kneaded product, the kneaded product was molded and then heated with high pressure steam at 150°C for 180 minutes. The bending strength is shown in Table 19, and the tensile strength is shown in Table 20 below. It is. In other words, the bending strength of melamine resin is 0.5% to 1.0%.
Although it has been significantly improved by 20%
It is the same as Production Example 8 that there is no significant improvement even when the compressive strength exceeds 30%.
Adding more than this will not improve much.

【table】

[Table] Production Example 10 Add a resin content of sulfonated melamine resin with a molecular weight of 80,000 and methylol melamine mixed in equal weights to the base concrete composition shown in Table 8 in Production Example 5 within a range of 0 to 35%. The flexural strength and compressive strength of each of the concrete molded bodies obtained were heat treated in the same manner as described above, and the results are shown in Table 21 below. It is clear that both bending and compression achieve a favorable strength improvement, but on the other hand, when the content exceeds 20%, the improvement is poor, and in particular, when the content exceeds 30%, there is almost no strength improvement.

[Table] In addition, we also examined changes in the materials according to the production examples described above. That is, representative examples include those containing 5% of sulfonated melamine resin, methylol melamine, and a mixture of equal weights thereof, and as comparative examples, those containing no resin content at all, and those containing the same resin content. Figures 1 and 2 of the attached drawings summarize changes in bending strength and compressive strength depending on material age for those that were cured in water at 20°C without being heat treated according to the method of the present invention. It is a diagram. In other words, Figure 1 shows the case where paste is used, and its composition is 100 parts of cement mixed with 1.5 parts of carbon fiber, with or without the addition of resin as described above, and the W/C is 22%. Figure 2 shows the case of concrete having the composition shown in Table 8 in Manufacturing Example 5. In the method of the present invention, the heat treatment was performed at 150°C.
High-pressure, high-temperature steam curing was performed at ℃ x 180 min, and thereafter the temperature was maintained at 60% and 20℃. However, when referring to such figures 1 and 2, the material of the present invention in figure 1 with paste is
In the case of 28 days, the bending strength was 150 to
It is ^about 300Kg/cm2 high, and the compressive strength is 200Kg/cm2.
This is an improvement of ^about 400Kg/cm2. Also, in the case of concrete shown in Figure 2, the bending strength of the concrete of the present invention is about 30 kg/cm ² higher than the comparative material cured in water (the raw material composition is exactly the same as the present invention), and the compressive strength is 300 kg/cm ² Although the degree is high, it is clear that the results can be obtained. "Effects of the Invention" According to the present invention as explained above, a sulfonated melamine resin is added and mixed in when producing a member using a hydraulic substance such as this kind of Portland cement, and the kneaded product is molded. This invention is industrially very effective because it is possible to improve the strength appropriately by heat-treating the resin, and to effectively improve the quality with the addition of a relatively small amount of resin.

[Brief explanation of the drawing]

The drawings show the technical contents of the present invention, and Figure 1 is a diagram summarizing the changes in compression and bending strength depending on the age of the material according to the present invention using paste and its comparative material. , FIG. 2 is a diagram summarizing the same relationships as in FIG. 1 for concrete according to the present invention and comparative materials.

Claims (1)

[Scope of Claims] 1. When adding and kneading Portland cement or other hydraulic inorganic powder, or aggregate or other compounding materials to the hydraulic inorganic powder, the molecular weight is 8000 to
1. A method for producing a hydraulic inorganic member, which comprises adding and mixing 200,000 sulfonated melamine resin, molding the product, and then heat-treating the product at room temperature or higher. 2. The hydraulic inorganic member according to claim 1, which uses as aggregate materials such as river sand and other fine aggregates, coarse aggregates, or fiber materials that do not change in quality at temperatures of at least about 200°C. Production method. 3. The method for producing a hydraulic inorganic member according to claim 1 or 2, wherein an anionic surfactant is also added and mixed during kneading. 4. The method for producing a hydraulic inorganic member according to any one of claims 1 to 3, wherein a polymer resin such as an acrylic emulsion is also added and mixed. 5 Catalyst with one or more of naphthalene sulfonic acid, dodecylbenzenesulfonic acid, para-toluene sulfonic acid and their amine salts, butanol ester of phosphoric acid, butanol ester of tetrachlorphthalic acid, and inorganic salts. A method for manufacturing a hydraulic inorganic member according to any one of claims 1 to 4, which is used as a method.