JP3383473B2 - Method for producing hydraulic composite material - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a hydraulic composite material, and more particularly to a production method for improving the performance of a composite material by controlling the curing initiation time of a polymer mixed with a hydraulic main material. It is a thing.

[0002]

2. Description of the Related Art As a technique for improving the performance of hydraulic materials such as cement mortar and concrete, a method of mixing a polymer (polymer) with these hydraulic materials is known. As a method of modifying such a hydraulic material,
There are provided a method of mixing an aqueous polymer dispersion with a hydraulic material, a method of impregnating a polymer after the hydraulic material is cured, and the like.

However, the former method of mixing the water-based polymer dispersion with the hydraulic material cannot sufficiently obtain the effect of modifying the hydraulic material. Further, in the latter method of hardening the hydraulic material and then impregnating with the polymer, ordinary concrete is required to have a remarkable effect on mechanical properties and durability. Such a problem was pointed out.

In order to impregnate a hydraulic material with a polymer, the hydraulic material is usually placed in an airtight chamber, and the polymer is impregnated in a vacuum state. However, in such a manufacturing method, for example, when manufacturing a large-sized composite material such as a precast wall body used for the outer wall of a building, a very large vacuum facility is required, which is However, it was difficult to put it into practical use.

On the other hand, as one kind of this type of modifying method, there is also known a method of producing a composite material by mixing a liquid polymer, for example, an epoxy resin with concrete and curing them. Since such a method for modifying a hydraulic material does not require a large-scale facility, its practical application is expected. Therefore, recently, for the purpose of improving the bending strength, tensile strength and deformation performance of precast products, or reducing the drying shrinkage ratio, a thermosetting resin, for example, an epoxy resin was added to concrete,
Attempts have been made to combine concrete and resin.

[0006] However, when manufacturing this type of product, the manufacturing method that has been attempted hitherto has technical problems as described below.

[0007]

That is, when attempting to form a composite of concrete and an epoxy resin in a precast product, generally, in order to uniformly disperse the epoxy resin, before casting into a formwork, The epoxy resin is added to the cement mortar and mixed.

However, in the production method in which the epoxy resin is simply added and mixed into the cement mortar, the curing rate of the cement matrix due to the hydration reaction and the curing rate of the epoxy resin due to the cross-linking reaction are different, so that the curing of both is performed. It becomes a very difficult situation to make the reactions work in a well-balanced manner. In other words, although the hydration reaction of the cement matrix is much slower than the curing reaction of the epoxy resin, the curing reaction of the epoxy resin starts earlier than that of the cement, although the hydration reaction of the cement matrix is much slower, although it depends on the blending amount of both. Is
For example, in the manufacturing process of the precast products as described above, the curing of the epoxy resin is started during the pre-curing period, and the curing of the cement proceeds thereafter, which causes a problem that the setting of the cement is delayed. However, the performance as a composite material could not be fully exhibited.

Further, in particular, the epoxy resin is usually composed of a liquid main agent and a curing agent, and these two components are mixed and used, but the viscosity of the liquid main agent is considerably large,
When a curing agent is added to this, the curing of the main agent may start and the viscosity may further increase, which not only takes time to mix, but also curing starts when the two components are mixed, so that quick measurement can be performed. There was also the risk of making a light weight mistake, which was one of the factors that hindered the practical application of precast products manufactured in factories.

The present invention has been made in view of the above problems, and a first object of the present invention is to provide a method for producing a hydraulic composite material capable of sufficiently exhibiting the performance of the composite material. To provide. A second object of the present invention is to provide a method for producing a hydraulic composite material which can reduce the trouble and the occurrence of measurement errors.

[0011]

In order to achieve the above object, the present invention provides a method for producing a hydraulic composite material produced by mixing a hydraulic main material and a liquid polymer and curing them. in, with composing the polymer at those latent curing type, the hydraulic main member any time after the start curing, to manifest the latent curability of the polymer, before
It is characterized by controlling the curing time of the polymer . The hydraulic main material can be selected from cement, gypsum, and those in which aggregate is added. The latent curable polymer is composed of an epoxy resin main agent and a curing agent coated with a capsule film, and the latent curability of the polymer is manifested by any one of temperature, pressure and light irradiation. be able to.

[0012]

According to the method for producing a hydraulic composite material having the above structure,
The polymer is composed of latent-curing type, and the latent-curing property of the polymer is revealed at an arbitrary time after the initiation of hardening of the hydraulic main material, so that it is possible to meet the performance requirements of the composite material to be obtained. , Control the curing time of the polymer,
The effect of modifying the hydraulic main material by the polymer can be effectively exhibited. In addition, in the production method of the present invention, since a latent curing type polymer is used, even if the polymer and the hydraulic main material are mixed in advance, in this state, the curing of the polymer does not start, so urgent measurement is necessary. It becomes possible to sufficiently mix them without any problem, and the polymer can be uniformly dispersed in the hydraulic main material. According to the configuration of claim 2, since the hydraulic main material can be selected from cement, gypsum, and those added with an aggregate, it can be applied to precast products using cement mortar or concrete. It will be possible. Further, according to the configuration of claim 3, the latent curing type polymer is composed of an epoxy resin main agent and a curing agent coated with a capsule film,
Since the latent curability of the polymer is manifested by any one of temperature, pressure, and light irradiation, even if the main agent and the curing agent are mixed, the curing of the main agent is not started, and a large amount of these is previously prepared. It can be stored for a long period of time in the state of being mixed and liquefied.

[0013]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT A preferred embodiment of the present invention will be described in detail below with reference to the accompanying drawings. 1 and 2 show an embodiment of a method for producing a hydraulic composite material according to the present invention. In the embodiment shown in the drawing, cement mortar is used as a hydraulic main material and epoxy is used as a liquid polymer. The present invention is applied when a resin is used to produce a precast product. The method for producing a precast product shown in FIGS. 1 and 2 is roughly composed of a raw material mixing and kneading step (A) and a heat curing step (B) which is performed subsequent to this step (A).

In the raw material mixing and kneading step (A), the mixing and kneading of the cement mortar 10 and the latent curing type thermosetting resin, for example, the epoxy resin 12 are separately performed. When the cement mortar 10 is mixed and kneaded, cement, fine aggregate and water are put into the mixing tank 14 to prepare a mixture having a predetermined mixing ratio. In the mixing of the epoxy resin 12, the liquid resin base material 12a and the curing agent 12b coated with the fine microcapsule film 12c are weighed in predetermined amounts, and are stirred and mixed in the mixing tank 16 to have a predetermined ratio. A one-liquid type is prepared.

The encapsulating film 12c covering the outer periphery of the curing agent 12b is melted when a predetermined temperature is applied, and the curing agent 12b inside is released to the outside, that is, in this state, the latent curing type polymer is latent. The curability is manifested, and the melting temperature is set to, for example, 60 ° C. or higher. The melting temperature of the capsule film 12c can be controlled by changing the film thickness. That is, the latent curability of the latent curable polymer that employs the capsule film 12 can be controlled by the temperature when the film thickness is constant, and by changing the film thickness when the temperature is constant. You can control.

When the cement mortar 10 and the one-component epoxy resin 12 are prepared, they are further mixed in the mixing tank 1.
It is put into 8 and mixed by stirring. In such a raw material mixing and kneading step (A), the latent-curing thermosetting resin is composed of the liquid epoxy resin base 12a and the curing agent 12b covered with the capsule film 12c. , Even if these are mixed, the main agent 12a and the curing agent 12
Since it does not come into direct contact with b, the curing of the main agent 12a is not started.

Therefore, since the viscosity of the epoxy resin main agent 12a does not increase, mixing and stirring can be easily and sufficiently performed, the curing agent 12b can be uniformly dispersed in the main agent 12a, and the epoxy resin main agent 12a is coated with the capsule film 12c. The hardener 12b can be easily measured. In addition, the main agent 12a
Since curing of the main agent 12a does not start even if the curing agent 12b and the curing agent 12b are mixed, it is possible to store them in a one-liquefied state for a long time by mixing a large amount in advance, and the one-liquefied epoxy resin 12 can be cement mortar. Even if mixed to 10,
Since the curing of the resin 12 is not started, the mixing can be sufficiently performed, and the resin 12 can be uniformly dispersed in the cement mortar 10.

When the raw material mixing and kneading step (A) is completed as described above, the mixed and kneaded cement mortar 10 and the one-component epoxy resin 12 are cast in a mold 20 having a predetermined shape. Then, the heating and curing step (B) is performed. The heating and curing step (B) is a step similar to the steam curing used in a normal precast plant.
A heat treatment as shown in FIG.

The heat curing step (B) shown in FIG. 2 comprises a pre-curing period, a temperature increasing period, a maximum temperature maintaining period and a temperature decreasing period. The pre-curing period is a period from the placing of the cement mortar 10 and the epoxy resin 12 to the start of the main curing, at room temperature,
For example, it is carried out in the air at a temperature of about 20 ° C. for about 2 to 3 hours to avoid thermal deformation when the cement mortar 10 that does not solidify is rapidly heated.

The temperature rising period is a period in which the main curing is started and, for example, the temperature of the mold 20 is raised at a substantially constant speed while sending steam, and the cement mortar 10 is used.
Is performed at a constant speed of about 20 ° C./h in consideration of production efficiency and obstacles due to rapid heating. The maximum temperature maintaining period is a period in which the temperature inside the mold 20 is maintained at the maximum temperature for a predetermined time, and is until the heating is completed.

The maximum temperature at this time is set to, for example, 80 ° C. or lower. The temperature lowering period is a period in which the temperature of the mold 20 and the like gradually decreases after the heating is stopped, and is a period until the product is removed from the mold 20. When the heat curing step (B) is performed under the above conditions, in the case of the present embodiment, the capsule film 12c covering the curing agent 12b.
When a temperature of 60 ° C. or higher is applied to the film, the film 12c melts, so that the capsule film 12c melts and the curing agent 12b is released during the temperature rising period, and the curing agent 12b and the main agent 12a come into contact with each other. The curing of the main agent 12a is started in the middle of the temperature rising period.

More specifically, in the case of the present embodiment, since the temperature of the heating atmosphere and the temperature inside the mold 20 increase in the latter half of the temperature increasing period, the temperature in the mold 20 actually increases slightly. Curing of the main agent 12 is started at a time close to the maximum temperature maintaining period. In this case, the curing start timing of the main agent 12a can be changed by changing the temperature rising condition, or
It can be controlled appropriately by changing the film thickness of the capsule film 12c.

When the heating and curing step (B) is completed, the mold 20 is removed and the demolded precast product is then subjected to normal curing to become a finished product.
By the way, according to the method for producing a precast product configured as described above, the latent curing type epoxy resin 12 is added and mixed before the cement mortar 10 is placed in the mold 20, and the heat curing Epoxy resin 1 during the heating process
Since the curing of No. 2 is started, it becomes possible to simultaneously perform the curing by the hydration reaction of cement and the curing of the epoxy resin 12.

When the cement and the epoxy resin 12 are simultaneously cured in this manner, the function obtained by compounding them is effectively exhibited, and a high-strength precast product can be manufactured. In the case of this embodiment, the capsule film 12c coated with the curing agent 12b is used.
Is melted by heating during the temperature rising period in the heating and curing step (B), and therefore, the epoxy resin 12 is used in the normal precast product manufacturing process without any special method.
Can be cured to achieve a composite with it and cement mortar 10.

Here, in order to confirm the effects of the present invention as described above, the present inventors prepared a precast specimen under the conditions described below and evaluated the performance of the obtained specimen. . The material used for the cement mortar was a high-strength Portland cement with a part of which was replaced with silica fume, and an aminosulfonic acid-based high-performance AE water reducing agent was used as an admixture. It was set as 1.

As the epoxy resin, a latent curing type one-component epoxy resin compound product (manufactured by Asahi Kasei Corporation, trade name:
Novacure HX-3722, Main agent: Bisphenol A
Type epoxy resin, curing agent: imidazole modified product, capsule membrane thickness 2μ, melting temperature 60-70 ° C), and the weight% (P / C) of resin and cement is 0, 5, 10, 1.
It was set to 5,20.

[Table 1] The materials used were mixed according to JIS R5201 "Cement physical test method". The dimensions of all the specimens were 4.0 × 4.0 × 16.0 cm, and compaction was performed for 60 seconds by a vibrating table during molding. In the heating and curing process, the pre-curing period shown in FIG. 2 is 20 ± 2 ° C. and 65 ± 5% R.
H, the period was set to 0, 1, 6, 27 days, the gradient of constant speed temperature rise during the temperature rising period was 20 ° C./h, and the maximum temperature during the maximum temperature maintaining period was 80 ° C. for 2 hours. . Then, the temperature falling period (about 3
After a lapse of time, the subsequent air curing was continued until the age test.

Bending strength and compressive strength (according to JIS R5201) were measured as mechanical properties, and water absorption and porosity were measured as physical properties. The age of the test material was set to 7 days and 28 days (27 days).
3 to 5 show the measurement results of the bending strength of the obtained specimen. FIG. 3 shows the measurement results when the epoxy resin was not mixed and the heat curing was not performed. FIG. 4 shows the measurement result when the epoxy resin was mixed and the pre-curing was performed for 1 day, and FIG. 5 is the measurement result when the epoxy resin was mixed and the pre-curing was performed for 6 days.

From the measurement results shown in these figures, it is understood that the bending strength is improved when the epoxy resin is mixed in the cement mortar. Here, it should be particularly noted that, in the case of a composite material added with an epoxy resin, the pre-curing period is considerably longer than the period (several hours) set in the production of a conventional precast product, and is 6 days. That is, it was found that the bending strength on the 27th day was significantly improved over the bending strength on the 1st day.

6 to 8 show the measurement results of the compressive strength of the obtained specimen. FIG. 6 shows the measurement results when the epoxy resin was not mixed and the heat curing was not performed. FIG. 7 shows the measurement result when the epoxy resin was mixed and the pre-curing was performed for 1 day, and FIG. 8 is the measurement result when the epoxy resin was mixed and the pre-curing was performed for 6 days.

From the measurement results shown in these figures, it is found that even when the epoxy resin is mixed in the cement mortar, the heat-curing improves the compressive strength of the composite material, and if such curing is performed, It is possible to secure almost the same compressive strength as a cement mortar product when no epoxy resin is mixed. Table 2 below shows the measurement results of the water absorption of the obtained specimen.

[Table 2] In addition, the measurement result of this water absorption rate has shown the average value of three test samples.

As is apparent from the measurement results, the composite material containing the latent curing type epoxy resin has a water absorption of 1 or less.
It can be seen that it decreases to about / 3. Table 3 below shows
The measurement result of the porosity of the obtained specimen is shown.

[Table 3] In addition, the measurement result of the porosity indicates an average value of three test pieces.

As is apparent from the measurement results, the composite material containing the latent curing type epoxy resin has a porosity of 1 or less.
It can be seen that the value greatly decreases to about / 3. Figure 9
The other Example of the manufacturing method of the hydraulic composite material concerning this invention is shown. In the embodiment shown in the figure, similarly to the above-mentioned embodiment, cement mortar 10 is used as the hydraulic main material, and the polymer is a liquid resin main agent 12a and a curing agent coated with a fine microcapsule film 12c. 12b is used to mix these components to produce a columnar precast product. At this time, the precast products
The hollow cylindrical sheath 20 is embedded at an appropriate position.

In the case of this embodiment, the cement mortar 10 is prepared without melting the microcapsule film 12c.
Only is cured. And cement mortar 10
When is cured and a predetermined strength is developed, the prestressed steel material 22 is inserted into the sheath 20, and a tensile force is introduced into this. When tension is introduced into the prestressed steel material 22, a compressive force is applied to the hardened cement mortar 10, and the compressive force causes the microcapsules 12c to rupture and the hardening reaction of the epoxy resin base material 12a to start.

That is, in the case of this embodiment, the latent curability of the latent curable polymer (one-pack type epoxy resin) becomes apparent when the curing reaction of the hydraulic main agent (cement mortar 10) is almost completed. Be converted. In this way, when the hydraulic main agent and the latent curable polymer are compounded, mutual curing reactions are performed separately, and one curing reaction has no effect on the other curing reaction. It is possible to effectively exert the modifying effect of the hydraulic material by the parimer.

In the above examples, the latent curing thermosetting resin is exemplified by the epoxy resin, but the practice of the present invention is not limited to this. It can also be applied to, for example, urethane resin, MMA (methylmethacrylate resin), polyester resin, phenol resin, etc. in which the curing reaction is started.

In the above embodiment, the means for imparting latent curability to the polymer is shown by surrounding the curing agent 12b with the microcapsules 12c, but the practice of the present invention is not limited to this. No, for example, a curing agent that does not dissolve at room temperature is granulated and mixed with the main agent, and when heating is desired to cure, a retarder that delays the curing reaction of the polymer is mixed and the curing reaction of the polymer is delayed by the retarder. May be controlled.

Further, the latent curability of the latent curable resin utilizing the microcapsule film 12c is not only revealed by the heat melting shown in the above-mentioned embodiment, but also, for example, it is placed in the mold 20. In this state, by applying pressure from above, the capsule membrane 12c can be destroyed and made visible, or an expansive material is mixed in,
The film 12c may be ruptured and exposed by the expansion of the expansion material, or may be exposed by irradiating ultraviolet rays or infrared rays from the surface.

Further, although cement mortar 10 is exemplified as the hydraulic main material in the above-mentioned embodiment, the present invention is not limited to this, and it can be mixed with gypsum, for example.

[0039]

As described above in detail in the embodiments,
According to the method for producing a hydraulic composite material of the present invention, the curing time of the polymer is controlled, so that the effect of modifying the polymer can be effectively exhibited. Further, in the production method of the present invention, since a latent curable polymer is used, even if the polymer and the hydraulic main material are mixed in advance, in this state,
The curing of the polymer does not start, and there is no need to rush the measurement, it becomes possible to thoroughly mix them, and the polymer can be uniformly dispersed in the hydraulic main material. Claim 2
According to the constitution, since the hydraulic main material can be selected from cement, gypsum, and those in which aggregate is added,
It can be applied to pre-cast products using cement mortar and concrete. Further, according to the constitution of claim 3, the latent curable polymer is composed of an epoxy resin main agent and a curing agent coated with a capsule film, and the latent curability of the polymer is manifested by temperature,
Since either the pressure or light irradiation is performed, even if the main agent and the curing agent are mixed, the curing of the main agent does not start, and a large amount of these are mixed in advance and stored for a long time in a liquid state. It can be used for products that are produced in large quantities in the factory.

[Brief description of drawings]

FIG. 1 is a process explanatory diagram when a manufacturing method according to the present invention is applied to manufacturing a precast product.

FIG. 2 is a time chart diagram of a heat treatment period of a heat curing step in the manufacturing shown in FIG.

FIG. 3 is a graph showing the measurement results of the bending strength of a test piece prepared without mixing a polymer and without heat curing.

FIG. 4 is a graph showing the measurement results of the bending strength of a test piece that was heat-cured after mixing a polymer and performing pre-curing for 1 day.

FIG. 5 is a graph showing the results of measuring the bending strength of a test piece that was heat-cured after mixing a polymer and performing pre-curing for 6 days.

FIG. 6 is a graph showing the measurement results of the compressive strength of a test piece prepared without mixing a polymer and without heat curing.

FIG. 7 is a graph showing the results of measurement of the compressive strength of a test piece that was heat-cured after mixing a polymer and performing pre-curing for 1 day.

FIG. 8 is a graph showing the measurement results of the compressive strength of a test piece that was heat-cured after mixing a polymer and performing pre-curing for 6 days.

FIG. 9 is a cross-sectional explanatory view showing another embodiment of the method for producing a hydraulic composite material according to the present invention.

[Explanation of symbols]

10 Cement mortar 12 Epoxy resin (latent curing type thermosetting resin) 12a Resin base 12b Curing agent 12c Capsule film 20 Form (A) Mixing and kneading process (B) Heat curing process

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshimasa Hayashi 4-640 Shimoseido, Kiyose-shi, Tokyo Inside Obayashi Technical Research Institute (72) Haruka Ogawa 4-640 Shimoseido, Kiyose-shi, Tokyo Obayashi Technical Research Co. In-house (72) Inventor Ichibo Mitani 4-640 Shimoseido, Kiyose-shi, Tokyo In-house Obayashi Institute of Technology (72) Inventor Masao Kawahara 1-10-10 Minamidai, Kawagoe-shi, Saitama Within Shock Beton Japan (56) References JP-A-1-203253 (JP, A) JP-A-50-126715 (JP, A) JP-A-6-321595 (JP, A) JP-A-5-58699 (JP, A) (58) Survey Areas (Int.Cl. ⁷ , DB name) C04B 28 / 02,24 / 24

Claims (3)

(57) [Claims] 1. A method for producing a hydraulic composite material, which is produced by mixing a hydraulic main material and a liquid polymer and curing them, wherein the polymer is a latent-curing type. , The latent curability of the polymer is revealed at any time after the initiation of curing of the hydraulic main material, and the hardness of the polymer is hardened.
A method for producing a hydraulic composite material, which comprises controlling the timing of conversion . 2. The method for producing a hydraulic composite material according to claim 1, wherein the hydraulic main material is selected from cement, gypsum, and those obtained by adding an aggregate to them. 3. The latent curable polymer is composed of an epoxy resin main agent and a curing agent coated with a capsule film, and the latent curability of the polymer is manifested by any of temperature, pressure and light irradiation. The method for producing a hydraulic composite material according to claim 1 or 2, wherein the method is performed by one of them.