JPWO2017099188A1 - Herbicidal material and method of use - Google Patents

Abstract

To provide a herbicidal material having a short curing time, high initial strength development, imparting initial frost damage and cracking resistance, reducing mowing labor, and ensuring the sustainability and environmental conservation of herbicidal protection and its usage. . A herbicidal material comprising calcium aluminate and soil. Further, it preferably contains cement, further contains gypsum, further contains shrinkage reducing agents and / or fibers, and further contains calcium silicate, and the calcium aluminate in the herbicidal material is CaO. A preferred herbicidal material having a / Al2O3 molar ratio of 1.0 to 3.0 and an impurity content of 15% by mass or less. A method of using a herbicidal material that is spread over the ground and sprayed with water, or mixed with water and spread over the ground.

Description

  The present invention relates to a herbicidal material that suppresses the growth of weeds such as river banks, paddy fields, or slopes of embankments such as railways and roads, and a method of using the same.

Weeds flourished on bank slopes on river banks, railways, roads, and on the banks of fields, and frequent mowing and herbicide spraying were necessary. Since grass cutting requires a great deal of labor, generally a method of spraying a herbicide is performed.
However, spraying herbicides is not a drastic measure because it needs to be sprayed frequently only by withering the grass. In addition, a method of sprinkling and spraying a herbicidal material containing cement has been proposed, but it takes time to cure, and it cannot be applied if it rains, so it flows before curing. Problems that cause initial frost damage and shrinkage cracks. Furthermore, since alkaline is high by containing cement and hexavalent chromium is contained, there also existed a subject also in the environmental influence.

In addition, a herbicidal material and a method for suppressing it by spraying or mixing a magnesium oxide-based solidified material not containing cement into the soil and watering and solidifying it have been proposed. (Patent Documents 1, 2, and 3)
In Patent Document 1, weed prevention material consisting mainly of magnesium oxide and blast furnace slag is mixed with soil on the ground surface, pressed and pressed, and sprinkled on it. Since expression is low, it is easy to be washed away by rainfall after construction, and the effect of suppressing weeds in the breeding season is likely to be reduced.

  Since Patent Documents 2 and 3 are the same magnesium oxide solidified material as Patent Document 1, the initial strength development is low, and the effect of suppressing weeds in the breeding season is likely to be reduced. Furthermore, the problem with these magnesium oxide-based herbicides in general is that because of the long curing time, the slope with a strong slope may not be able to reach a certain thickness due to watering during construction or raining during rainfall. There was a case where it did not harden in some places. In addition, since the initial strength development is low, plants such as cedar, reed, cocoon, and chigaya that have high penetrating ability are likely to penetrate and grow easily.

  Patent Document 4 is characterized in that aggregates of incinerated ash, slag, and coal ash are spread, and chloroprene latex, ethylene vinyl acetate copolymer emulsion, and acrylic emulsion solidifying material are sprayed thereon and fixed. This is an environmentally friendly herbicide that does not use cement or basic substances. However, since it is necessary to spread the latex and emulsion uniformly on the thickness of 3 to 20 cm by human power and heavy machinery, much labor is required.

JP 2003-47388 A JP 2007-330114 A JP 2014-51849 A JP 2014-234655 A

  The present invention has a short curing time, high initial strength development, imparts initial frost damage and crack resistance, reduces environmental burden, reduces mowing effort, and ensures sustainability and environmental conservation of grass protection. A herbicidal material and a method of using the same are provided.

That is, the gist of the present invention is as follows.
(1) A herbicidal material containing calcium aluminate and soil, (2) a herbicidal material of (1) further containing cement, (3) further containing gypsum (1) or Anti-weed material (2), (4) calcium aluminate, a CaO / _Al 2 _{O 3} molar ratio 1.0 to 3.0, the content of impurities is not more than 15 wt% (1) - (3) the herbicidal material, (5) the calcium aluminate has a Blaine specific surface area value of 3000 cm ² / g or more, (1) to (4) the herbicidal material, and (6) the calcium aluminate vitrification rate. (1) to (6), wherein the herbicidal material of (1) to (5) is 70% or more, and (7) the cement content is 100 to 40000 parts by mass with respect to 100 parts by mass of calcium aluminate. ) Herbicide, (8) gypsum content is calcium aluminate 1 (1) to (6) herbicide which is 50 to 250 parts by mass with respect to 0 part by mass, (9) (1) to (6) herbicide further containing calcium silicate, (10) The calcium silicate is γ-2CaO · SiO ₂ (9) herbicide, (11) the content of calcium silicate is 10 to 60 parts by mass with respect to 100 parts by mass in total of calcium aluminate and gypsum. (9) or (10) herbicidal material, (12) further containing a shrinkage reducing agent and / or fiber (1) to (11) herbicidal material, (13) shrinkage reducing agent content. (12) the herbicidal material of 0.5 to 20 parts by mass with respect to a total of 100 parts by mass of calcium aluminate and gypsum, (14) and (1) to (13) Material, (15) the content of fiber is calcium aluminate and gypsum A total of 100 parts by mass of 0.05 to 5 parts by mass of (14) herbicidal material and (16) (1) to (15) herbicidal material are spread on the ground and sprinkled on the ground to cover them. How to use herbicides. (17) A method of using a herbicidal material, wherein the herbicidal material according to any one of (1) to (15) is kneaded with water and spread on the ground to cover it. (18) The usage method of the herbicidal material of (16) or (17) whose usage-amount of water is 5-100 mass parts with respect to 100 mass parts of herbicidal materials.

  The herbicidal material of the present invention has a short curing time, high initial strength development, excellent initial frost damage and crack resistance, and has a sufficient herbicidal effect. By using the herbicidal material of the present invention, the labor of mowing can be reduced, and the sustainability and environmental conservation of the weeding can be ensured.

The calcium aluminate used in the present invention is mainly composed of CaO and Al ₂ O ₃ obtained by mixing a calcia raw material and an alumina raw material and firing the kiln or melting and cooling in an electric furnace. It is a general term for substances having hydration activity, and can be used either crystalline or amorphous. It is a material with a fast curing time and high initial strength development. A typical example of calcium aluminate is alumina cement, and a commercially available product can be usually used. For example, alumina cement 1 and alumina cement 2 can be used. Of these, amorphous calcium aluminate that is hardened in a shorter time than alumina cement and has a high initial strength after that is rapidly cooled after melting.
Among calcium aluminates, the molar ratio of CaO to Al ₂ O ₃ (CaO / Al ₂ O ₃ molar ratio) is preferably 1.0 to 3.0, and more preferably 1.7 to 2.5. When the molar ratio is 1.0 to 1.7, it is possible to further shorten the curing time and increase the initial strength by adding cement, slaked lime and quicklime.

In the present invention, the impurity contained in the calcium aluminate is preferably 15% by mass or less from the viewpoint of initial strength development, and more preferably 10% by mass or less. Here, the impurities refer to substances other than CaO and Al ₂ O ₃ . When the impurity exceeds 15% by mass, it takes time to cure and may not solidify at a low temperature. Typical examples of impurities include silicon oxide, magnesium oxide, and sulfur oxide. Besides, organic substances, alkali metal oxides, alkaline earth metal oxides, titanium oxide, iron oxide, alkali metal halides, alkaline earths. There are metal halides, alkali metal sulfates, alkaline earth metal sulfates and the like in which CaO or Al ₂ O ₃ is partially substituted or dissolved. However, it is not limited to these.

The vitrification rate of the calcium aluminate used in the present invention is preferably 70% or more, more preferably 90% or more in terms of reaction activity. If the vitrification rate is less than 70%, the initial strength development may be lowered. The vitrification rate of calcium aluminate is preferably 70% or more, more preferably 90% or more in terms of reaction activity. The vitrification rate is determined by measuring the main peak area S of the crystal mineral in advance by powder X-ray diffractometry for the measurement sample, heating at 1000 ° C. for 2 hours, and then slowly cooling at a cooling rate of (1 to 10 ° C.) / Min. Then, the main peak area S ₀ of the crystal mineral after heating by the powder X-ray diffraction method is obtained, and the vitrification ratio χ is calculated by using the following equation using the values of S ₀ and S.
Vitrification rate χ (%) = 100 × (1−S / S ₀ )
The particle size of the calcium aluminate, in terms of initial strength development is preferably more than Blaine specific surface area ^{3000cm 2 / g, 5000cm 2 /} g or more is more preferable. If it is less than 3000 cm ² / g, the curing time becomes long and the initial strength development may be lowered.

The cement used in the present invention is usually a variety of Portland cements, such as early strength, very early strength, low heat or moderate heat, mixed cements such as blast furnace slag, fly ash and silica fume mixed with these cements, urban Examples include environmentally friendly cement (eco-cement) manufactured from waste incineration ash and sewage sludge incineration ash, and commercially available fine particle cement. Here, it is assumed that the cement does not include alumina cement which means calcium aluminate.
These various cements and various mixed cements can be used in the form of fine powder. Moreover, what was prepared by increasing / decreasing the quantity of components (for example, gypsum etc.) normally used for cement can also be used. These cements can be used alone or in combination of two or more. Among these, blast furnace cement is preferable because of its low hexavalent chromium content.
When using cement by this invention, the usage-amount is 100-40000 mass parts with respect to 100 mass parts of calcium aluminates, and 20-1000 mass parts is more preferable. If the amount used is less than 100 parts by mass, working time may not be obtained, and early curing that exceeds 40000 parts by mass may not be obtained.

  As the gypsum used in the present invention, hemihydrate gypsum or anhydrous gypsum can be used. Anhydrous gypsum is preferable in terms of strength development, and hydrofluoric acid byproduct anhydrous gypsum and natural anhydrous gypsum can be used. The pH when the gypsum is immersed in water is preferably from a weak alkali having a pH of 8 or less to acidic. When the pH is high, the solubility of the gypsum component becomes high, which may inhibit the initial strength development. The pH here refers to the pH of the diluted slurry at 20 ° C. of gypsum / ion exchange water = 1 g / 100 g measured with an ion exchange electrode or the like. Such pH is preferably 3-8, more preferably 5-7.

The particle size of the gypsum, preferably 3000 cm ² / g or more in Blaine specific surface area value, from the viewpoint of the 5000 cm ² / g or higher initial strength development, the proper work time is obtained. The specific surface area value is usually 30000 cm ² / g or less, and preferably 20000 cm ² / g or less from the viewpoint of obtaining an appropriate working time.
The amount of gypsum used (containing) is preferably 50 to 250 parts by mass, more preferably 70 to 200 parts by mass, with respect to 100 parts by mass of calcium aluminate. When the amount used is less than 50 parts by mass, working time cannot be obtained, and strength development may be reduced. On the other hand, if it exceeds 250 parts by mass, sufficient working time can be taken, but initial strength may not be obtained.

The shrinkage reducing agent used in the present invention prevents the unreacted moisture from escaping and suppresses the drying shrinkage of cement hydrate. The main components are roughly classified into lower alcohol alkylene oxide adducts, alcohols. Glycol-based, glycol ether / amino alcohol derivative-based, polyether-based, low molecular weight alkylene oxide copolymer systems and the like are preferable. As the shrinkage reducing agent, one kind or a mixture of two or more kinds can be used, and either a liquid form or a powder form can be used.
The shrinkage reducing agent may be kneaded in advance with the herbicidal material before water is applied, or may be sprinkled with water mixed with water sprayed on the herbicidal material spread on the ground. Furthermore, it may be added when kneading the herbicidal material and water, or it may be spread on the surface after the herbicidal material has reacted with water and hardened, and its method of use is not particularly limited.

As shrinkage reducing agents, commercially available products can be used. Typical examples include SK Guard manufactured by Denka, Hibigad and Shrink Guard manufactured by Floric, Hibidan manufactured by Takemoto Yushi Co., Ltd., and Taiheiyo Cement. Examples include “Tetragard”.
The amount of the shrinkage reducing agent used is preferably 0.5 to 20 parts by mass and more preferably 0.7 to 10 parts by mass with respect to 100 parts by mass of calcium aluminate and gypsum or 100 parts by mass of cement. If the amount used is less than 0.5 parts by mass, the effect of suppressing cracking may be low, and if it exceeds 20 parts by mass, the strength may not be obtained.

The fibers used in the present invention improve crack resistance. Examples of the fibers include polymer fibers such as vinylon fibers, propylene fibers, and nylon fibers, metal fibers such as steel fibers, glass fibers, and steel fibers, or inorganic fibers typified by carbon fibers. Of these, vinylon fiber, propylene fiber, and nylon fiber are preferable.
The amount of fibers used is preferably 0.05 to 5 parts by mass, more preferably 0.08 to 2.0 parts by mass with respect to 100 parts by mass as a total of calcium aluminate and gypsum or 100 parts by mass of cement. If the amount used is less than 0.05 parts by mass, the effect of improving crack resistance may not be exhibited, and if it exceeds 5 parts by mass, the viscosity may increase and workability may deteriorate. The length of the fiber is preferably 15 mm or less, and more preferably 10 mm or less from the viewpoint of the beauty of the iron finish surface.

In the present invention, calcium silicate can be used for the purpose of enhancing the long-term strength of the herbicidal material. Calcium silicate has a 3CaO · _{SiO 2} or 3CaO · 2SiO ₂ and 2CaO · SiO ₂ and CaO · SiO _2, these things any crystalline phase can be used, may be mixed these two or more, in particular It is not limited. Since γ-2CaO · SiO ₂ reduces carbonation shrinkage caused by absorption of carbon dioxide in the air, crack resistance is improved, which is most preferable.
As 2CaO · SiO ₂ , γ-2CaO · SiO ₂ is known as a low temperature phase, and is different from α-2CaO · SiO ₂ and β-2CaO · SiO ₂ which are high temperature phases. These are both 2CaO · SiO ₂ and have the same chemical composition, but their crystal structures are different.
2CaO · SiO ₂ present in the cement clinker is β-2CaO · SiO ₂ . Although β-2CaO · SiO ₂ has hydraulic properties, γ-2CaO · SiO ₂ does not have hydraulic properties, but the present inventors have found that it has a property of absorbing and curing carbon dioxide in the atmosphere. .

The particle size of the calcium silicate to be used in the present invention is preferably 3000 cm ² / g or more in Blaine specific surface area value, 4,000~8,000cm ² / g is more preferable. When the Blaine specific surface area value is less than 3,000 cm ² / g, carbon dioxide in the atmosphere is absorbed and the reaction is not sufficient, and crack resistance may not be sufficiently obtained. Even if it exceeds 8,000 cm ² / g, further enhancement of the effect cannot be expected.
The amount of calcium silicate used is preferably 10 to 60 parts by mass and more preferably 20 to 50 parts by mass with respect to 100 parts by mass in total of calcium aluminate and gypsum. If it is less than 10 parts by mass, the effect of suppressing cracking may be low. If it exceeds 60 parts by mass, further enhancement of the effect cannot be expected.

  The soil (also referred to as soil) used in the present invention includes one or more of gravel, sand, gravel, and clay, and is not particularly limited. Sandy soil such as mountain sand, river sand, sea sand, silty soil, clayey soil, residual soil generated from construction, lightweight aggregate, recycled aggregate, volcanic ash and slag aggregate, etc. Any of them can be used, such as using the soil of the place as it is. In general, natural sand, red sand, red swamp, kanuma earth, and dry sand are more preferable because of their stable quality.

  In the herbicidal material of the present invention, the amount of soil used is usually preferably 100 to 1000 parts by weight, more preferably 200 to 800 parts by weight, with respect to 100 parts by weight of calcium aluminate and gypsum or 100 parts by weight of cement. Preferably, 200-700 mass parts is more preferable. If the amount used is less than 100 parts by mass, the strength development is high but economically unpreferable, and if it exceeds 1000 parts by mass, the strength is low, the initial frost damage property is inferior, and there is a possibility of being dented.

  In the present invention, the setting modifier can be used within a range not impairing the object of the present invention. The setting modifier is not particularly limited as long as it accelerates or delays the setting of the cement. Specifically, alkali hydroxide, alkali metal chloride salt, alkali metal carbonate, oxycarboxylic acid or salt thereof, phosphoric acid or salt thereof, dextrin, sucrose, polyacrylic acid or salt thereof, water reducing agent, high performance One or more water reducing agents can be used.

  Furthermore, in the herbicidal material of the present invention, solidified materials having a low pH such as magnesium oxide, bulking agents such as wood chips, rubber chips, rice husks, various portland cements, calcium hydroxide, calcium chloride, fine limestone powder, fly Adhesive materials such as ash, kaolin, shirasu, diatomaceous earth, silica fume, foaming agents, antifoaming agents, thickeners, rust preventives, antifreeze agents, water reducing agents, fluidizing agents, polymers, clay minerals such as bentonite, hydrotalcite It is possible to use 1 type (s) or 2 or more types, such as anion exchangers, coloring agents, etc. in the range which does not inhibit substantially the objective of this invention.

The mixing of each component material in the herbicidal material of the present invention is not particularly limited, and the respective materials may be mixed at the time of construction, or a part or all of them may be mixed in advance. . In particular, it is preferable in terms of quality to mix each component material in advance and to mix water on site. When mixing in advance, the soil is preferably dry. Moreover, the soil of the place which performs a herbicidal treatment can also be used as it is.
5-100 mass parts is preferable with respect to the total 100 mass parts of the herbicidal material of this invention, and, as for the usage-amount of the water in the herbicidal material of this invention, 7-50 mass parts is more preferable. If it is less than 5 parts by mass, mixing may be difficult, and if it exceeds 100 parts by mass, strength may not be obtained.
As each component material mixing apparatus, an existing apparatus can be used. For example, a tilting cylinder mixer, an omni mixer, a two-axis forced mixer, a Henschel mixer, a V-type mixer, and a Nauta mixer can be used.

  As a method of using the herbicidal material of the present invention, the weeds on the ground are mowed to a size of preferably about 1 cm or less, more preferably 0.5 cm or less with a mower or the like, and the weeds are spread after removing the cut weeds. There are a method of spraying and covering the ground with weeds, and a method of spraying a mixed herbicide on the ground where weeds are growing. More preferably, the weeds on the ground are mowed and then a herbicide is sprayed thereon before covering.

  In the case where the herbicidal material of the present invention is spread over the ground where the grass has been mowed, and the surface is sprinkled to solidify the surface, the method is to spread the herbicidal material over the ground and sprinkle the water with a watering device or the like. Is preferred. The thickness to spread is preferably 1 to 5 cm, and more preferably 2 to 4 cm. If the thickness is less than 1 cm, it becomes difficult to cover the entire ground surface, so that the herbicidal effect may be reduced. If it exceeds 5 cm, the material cost is high, but the material cost is high. It is not preferable.

  When the herbicidal material of the present invention is laid on the ground that has not been soiled or on the ground that is not mowing, and mixed and stirred with the soil on the ground, it is mixed and stirred using a machine such as a backhoe or a stabilizer. It is possible. In this case, it is possible to obtain a hard ground by further rolling after mixing and stirring.

  Hereinafter, the present invention will be described in detail based on experimental examples, but the present invention is not limited to these experimental examples.

"Experiment 1"
100 parts by mass of calcium aluminate shown in Table 1 was mixed with 100 parts by mass of gypsum, and the setting time, compressive strength, and initial frost damage were measured.
500 parts by mass of soil is added to 100 parts by mass of calcium aluminate and gypsum shown in Table 1, and 0.3 liter of sodium citrate is used as a coagulation adjusting agent for a total of 100 parts by mass of calcium aluminate, gypsum and soil. A herbicidal material was prepared by adding parts by mass. After laying this herbicidal material on the formwork, 15 parts by mass of water was sprayed on a total of 100 parts by mass of calcium aluminate, gypsum and soil to prepare a test specimen. The results are also shown in Table 1.

  For comparison, mortar and magnesia-based solidified material using ordinary cement were prepared. (-Company) Dry mortar with 3/1 mass ratio of standard sand made by Cement Association and ordinary cement was laid on the mold and sprinkled with water so that (water / ordinary cement ratio) was 50% by weight A material was prepared. The magnesia-based solidified material is a mixture of 500 parts by mass of soil mixed with 100 parts by mass of commercially available magnesium oxide obtained by firing Chinese magnesium. On the other hand, 20 parts by mass of water was sprayed to prepare a herbicide. The results are also shown in Table 1.

<Materials used>
-Calcium aluminate: By changing the CaO / Al ₂ O ₃ molar ratio of calcium carbonate and aluminum oxide, adding silica, melting at 1650 ° C and quenching, vitrification rate 97%, Blaine specific surface area value 5000 cm ² A calcium aluminate having an impurity of silica was prepared.
Gypsum: natural anhydrous gypsum, Blaine specific surface area value 5000 cm ² / g
・ Soil: Pure sand from Aichi Prefecture, 5mm sieve ・ Alumina cement: Alumina cement No. 1, manufactured by Denka ・ Coagulation modifier: Anhydrous sodium citrate, Kamata Chemical Industries ・ Water: Tap water ・ Normal cement: Normal Portland cement (Denka)
・ Sand: Standard sand made by Cement Association ・ Magnesia solidified material: Commercially available magnesium oxide fired from Chinese magnesium

<Measurement method>
-Curing time: The time when it does not dent even if it pushes the kneaded herbicide with a finger was measured.
-Compressive strength: The uniaxial compressive strength produced the 4x4x16cm test piece according to JISR5201 in the environment of 20 degreeC and 60% of relative humidity. The strength of the material was measured for 6 hours and 28 days, and the curing method was an air drying curing under an environment of 20 ° C. and a relative humidity of 60%.
-Initial frost damage resistance: After preparing a specimen by the same method as compressive strength in an environment of 20 ° C. and a relative humidity of 60%, the specimen was immediately cured in a −10 ° C. environment until a material age of 7 days. Then, after air drying and curing in an environment of 20 ° C. and 60% relative humidity until the age of 28 days, the strength was measured, and the strength of the strength relative to the 28-day strength value that was always mixed and cured in an environment of 20 ° C. The percentage (%) was calculated. Furthermore, the presence or absence of cracks on the surface of the specimen was confirmed.
-PH: After preparing a specimen in an environment of 20 ° C. and a relative humidity of 60% in the same manner as the compressive strength, the specimen at the age of 28 days was pulverized and the supernatant stirred for 30 minutes with 100 times pure water The pH of the liquid was measured.
-Hexavalent chromium elution amount: After preparing a specimen in an environment of 20 ° C and a relative humidity of 60% by the same method as the compressive strength, the specimen at the age of 7 days was measured based on the Environmental Agency Notification No. 46 method .

  From Table 1, it can be seen that the herbicidal material of the present invention has a short curing time, high initial strength development, excellent initial frost damage resistance, low pH and hexavalent chromium elution amount, and excellent environmental impact.

"Experimental example 2"
Using the calcium aluminate of Experiment No. 1-4 of Experimental Example 1, changing the ratio of calcium aluminate and gypsum at the ratios shown in Table 2, and further, with respect to a total of 100 parts by mass of calcium aluminate and gypsum, This was performed in the same manner as in Experimental Example 1 except that the ratio was changed. The results are shown in Table 2.

  From Table 2, it can be seen that the herbicidal material of the present invention has a short curing time, high initial strength, and excellent initial frost damage resistance.

"Experiment 3"
About the herbicidal material of Experiment No. 1-4 of Experimental Example 1, the shrinkage reducing agents A and B, fibers, and calcium silicates A, B, and C described below are mixed at the ratio shown in Table 3, and the dry shrinkage ( Measurement of length change rate), a herbicidal test, and a crack test were performed.
For comparison, the same test was performed on the mortar (experiment No. 1-8) using the normal cement used in Experimental Example 1 and the magnesia-based solidified material (experiment No. 1-9). The results are also shown in Table 3.

<Materials used>
Shrinkage reducing agent A: copolymer of low molecular weight ethylene oxide and propylene oxide, manufactured by Denka Co., Ltd., trade name SKGard / shrinkage reducing agent B: polyoxyalkylene derivative system, powder, manufactured by NOF Corporation, trade name: DSP- E40 "
-Fiber: Vinylon fiber, fiber length 6 mm, fiber diameter 0.027 mm, convergence type-Calcium silicate A: 3 Calcium carbonate of 3CaO.SiO ₂ reagent and 1 mol of silicon dioxide are mixed and pulverized, and then fired in an electric furnace. Synthesized. Blaine specific surface area value 1800 cm ² / g.
Calcium silicate B: 2 mol of calcium carbonate and 1 mol of silicon dioxide of β-2CaO · SiO ₂ reagent were mixed and pulverized, and then sintered in an electric furnace and synthesized. Blaine specific surface area value 1800 cm ² / g.
Calcium silicate C: After mixing and grinding 2 mol of calcium carbonate and 1 mol of silicon dioxide of γ-2CaO · SiO ₂ reagent, they were synthesized by firing in an electric furnace. Blaine specific surface area value 1800 cm ² / g.
・ Water: Tap water ・ Soil: Pure sand from Aichi Prefecture, 5mm sieve

<Measurement method>
Drying shrinkage (length change rate): Specimen sprinkled 15 parts by weight of water with respect to 100 parts by weight of each herbicide, and JIS A 1129-3 mortar and concrete length change test method In accordance with the dial gauge method, the length change rate after 180 days of material was measured at a temperature of 20 ° C. and a relative humidity of 60% based on the material age of 2 days.
・ Weed control test ・ Crack test: Weeds weeded in the field up to 0.5cm in length with a mower in advance, cultivated the field with a cultivator, and on top of that, tall fescue, Kentucky bluegrass, And the perennial ryegrass mixture was sprinkled with 40 g / m ² and stepped on the foot and rolled. On top of that, each herbicidal material was uniformly laid on the foundation surface with a thickness of 3 cm and an area of 5 m ² , then 15 parts by weight of water was sprayed on a total of 100 parts by weight of each herbicidal material, and 180 days later The number of cracks and the number of turf that grew from the surface of the herbicide were measured.

  From Table 3, it can be seen that the herbicidal material of the present invention is less cracked, has less turf, and has an excellent herbicidal effect. In addition, it can be seen that the herbicidal material of the present invention, when used in combination with a shrinkage reducing agent, fiber, and calcium silicate, reduces the amount of shrinkage, suppresses cracking, and suppresses turf. On the other hand, it can be seen that mortar and magnesia-based solidified material have large shrinkage, many cracks, and a lot of turf.

"Experimental example 4"
Experiment No. 3-17 experiment No. 3-17, No. 3-18, or No. 3-19 of each herbicidal material is put in an omni mixer, calcium aluminate, gypsum, shrinkage reducing agent, fiber, calcium silicate, and As with Experimental Example 3, except that 15 parts by mass of water was added to the omni mixer instead of watering, and the kneaded mixture was laid on the formwork or the base surface for a total of 100 parts by mass of the setting modifier. It carried out (Experiment No.4-1, No.4-2, No.4-3).
In addition, as a comparison, the mortar (experiment No. 1-8) using the ordinary cement used in Experimental Example 1 and the magnesia-based solidified material (Experiment No. 1-9) were also used in Experimental Example 1, respectively. It was carried out in the same manner as in Experimental Example 3 except that the kneaded mixture was laid on the formwork or foundation surface instead of watering. The results are also shown in Table 4.

  From Table 4, it can be seen that the herbicidal material of the present invention is less cracked and less grassy and has an excellent herbicidal effect even when a kneaded mixture is laid.

“Experimental Example 5”
A herbicidal material was prepared by adding 15 parts by mass of calcium aluminate shown in Table 5, 15 parts by mass of gypsum, 0.5 parts by mass of a coagulation modifier, and 600 parts by mass of soil with respect to 100 parts by mass of cement. After laying this herbicidal material on the mold, 20 parts by mass of water was sprayed on 100 parts by mass of cement to prepare a test specimen. The curing time, compressive strength, and initial frost damage were measured.
For comparison, mortar and magnesia-based solidified material using ordinary cement were prepared. The blending of mortar is (one company) laying dry mortar with 3/1 mass ratio of standard sand made by Cement Association and ordinary Portland cement on the formwork, and water so that the water / cement ratio is 50% by mass. A herbicide was prepared by watering. The magnesia-based solidified material is a mixture of 500 parts by mass of soil mixed with 500 parts by mass of commercially available magnesium oxide obtained by firing Chinese magnesium, and 20 parts by mass of water is sprinkled to form a herbicide. Prepared. The results are also shown in Table 5.

<Materials used>
-Calcium aluminate: Change the CaO / Al ₂ O ₃ molar ratio of calcium carbonate and aluminum oxide, add silica, melt at 1650 ° C, quench rapidly to a vitrification rate of 97%, and grind the Blaine specific surface area value It was set to 5000 cm ² / g. The impurity was silica and adjusted by changing its content.
Cement: Blast furnace type B cement, Blaine specific surface area value 3750 cm ² / g
Gypsum: natural anhydrous gypsum, Blaine specific surface area value 5000 cm ² / g
・ Soil: Aichi prefecture sand sand, 5mm sieve, Nagano prefecture river sand dry product, 1.2mm sieve under mixed equivalent ・ Alumina cement: Alumina cement No. 1, manufactured by Denka ・ Coagulation modifier: anhydrous sodium citrate, Made by Iwata Chemical Co., Ltd. ・ Water: Tap water ・ Normal cement: Normal Portland cement (Denka)
・ Sand: (One company) Standard sand made by Cement Association ・ Magnesia solidified material: Commercially available magnesium oxide calcined from China

<Measurement method>
-Curing time: The time when the mixed herbicidal material was not depressed even when pressed with a finger was measured.
・ Compressive strength: Uniaxial compressive strength conforms to the uniaxial compression test method of the stable treatment mixture in the environment of temperature 20 ℃ and relative humidity 60% (Pavement Test Method Handbook, Japan Road Association). A 127 mm cylindrical shape was prepared, and the specimens were divided into three layers, and each layer was struck with 25 sticks. The strength was measured 6 hours and 28 days after the specimen preparation. The curing method was an air-dried curing under an environment of 20 ° C. and a relative humidity of 60%.
-Initial frost damage resistance: Kneaded in the same manner as the compressive strength in an environment of 20 ° C. and 60% relative humidity, and immediately after the specimen was prepared, it was cured in a −10 ° C. environment until the age of 7 days. Then, after the material was air-dried in an environment of 20 ° C. and 60% relative humidity until the age of 28 days, the strength was measured, and the strength relative to the 28-day strength value that was constantly mixed and cured in an environment of 20 ° C. The percentage (%) was calculated. Furthermore, the presence or absence of cracks on the surface of the specimen was confirmed.

  From Table 5, it can be seen that the herbicidal material of the present invention has a short curing time, high initial strength, and excellent initial frost damage resistance.

"Experimental example 6"
As shown in Table 6, the same test as in Experimental Example 5 was performed except that the proportion of calcium aluminate and gypsum was changed with respect to 100 parts by mass of cement, and the proportion of soil was changed with respect to 100 parts by mass of cement. Carried out. The results are also shown in Table 6.

<Materials used>
Calcium aluminate: CaO / Al ₂ O ₃ molar ratio 2.2, vitrification rate 97%, Blaine specific surface area value 5000 cm ²

  From Table 6, it can be seen that the herbicidal material of the present invention has a short curing time, high initial strength, and excellent initial frost damage resistance.

"Experimental example 7"
About the herbicidal material of Experiment No. 1-4 of Experimental Example 5, the shrinkage-reducing agents A and B described below are mixed at the ratio shown in Table 7, and the amount of dry shrinkage (length change rate) is measured and the anti-shock material A grass / crack test was conducted.
For comparison, the same test was performed on the mortar (experiment No. 1-8) using the normal cement used in Experimental Example 5 and the magnesia-based solidified material (experiment No. 1-9). The results are also shown in Table 7.

<Materials used>
Calcium aluminate: CaO / Al ₂ O ₃ molar ratio 2.2, vitrification rate 97%, Blaine specific surface area value 5000 cm ²
・ Shrinkage reducing agent A: copolymer of low molecular weight ethylene oxide and propylene oxide, manufactured by Denka Co., Ltd., trade name: escagard / shrinkage reducing agent B: polyoxyalkylene derivative, powder, commercially available product, manufactured by Nippon Oil & Fats Co., Ltd .: product Name "DSP-E40"
・ Is: Vinylon fiber, fiber length 6mm, fiber diameter 0.027mm, convergence type, commercial product ・ Soil: Aichi prefecture pure sand, 5mm sieve, Nagano prefecture dried river sand, 1.2mm sieve

<Measurement method>
-Drying shrinkage (length change rate): Specimen sprinkled 20 parts by weight of water for a total of 100 parts by weight of each herbicidal material, and JIS A 1129-3 mortar and concrete length change test method Based on the dial gauge method, the rate of change in length after 30 days of age was measured at a temperature of 20 ° C. and a humidity of 60% based on the age of 2 days.
・ Weed control test ・ Crack test: Weeds weeded in the field up to 0.5cm in length with a mower in advance, cultivated the field with a cultivator, and on top of that, tall fescue, Kentucky bluegrass, A perennial ryegrass mixture was sprinkled at 40 g / m ² and stepped on and rolled. On top of that, each herbicidal material was uniformly laid on the foundation surface with a thickness of 3 cm and 5 m ² , then 20 parts by mass of water was sprayed on a total of 100 parts by mass of each herbicidal material, and the number of cracks after 180 days. The number of grass that grew from the surface of the herbicidal material was measured.

  From Table 7, it can be seen that the herbicidal material of the present invention is less cracked, has less turf, and has an excellent herbicidal effect. Further, it can be seen that when the herbicidal material of the present invention is used in combination with a shrinkage reducing agent and fibers, the amount of shrinkage is small, cracks are suppressed, and turf can be suppressed. On the other hand, it can be seen that mortar and magnesia-based solidified material have large shrinkage, many cracks, and a lot of turf.

"Experimental example 8"
For each of the herbicidal materials of Experiment No. 3-5, No. 3-6, and No. 3-7 in Experimental Example 7, the total of cement, calcium aluminate, gypsum, setting modifier, shrinkage reducing agent, fiber, and soil The test was conducted in the same manner as in Experimental Example 7 except that 20 parts by mass of water was added to an omni mixer instead of watering with respect to 100 parts by mass, and the kneaded mixture was laid on a formwork or a foundation surface (Experiment No. 4). -1, No. 4-2, No. 4-3).
For comparison, the mortar (experiment No. 1-8) using the ordinary cement used in Experimental Example 5 and the magnesia-based solidified material (Experiment No. 1-9) were also used in Experimental Example 5, respectively. The experiment was carried out in the same manner as in Experimental Example 7 except that the kneaded mixture was laid on the formwork or foundation surface instead of watering. The results are also shown in Table 8.

  From Table 8, it can be seen that the herbicidal material of the present invention is less cracked and less grassy and has an excellent herbicidal effect even when a kneaded mixture is laid.

  The herbicidal material of the present invention and the method of using the same have the effect of reducing the labor of mowing and ensuring the sustainability of the weeding, so that the river bank, the shore of the field, the railway, the road, etc. Growth of weeds such as the slope of embankment can be suppressed. Further, the herbicidal material of the present invention has a low elution pH and a low elution amount of hexavalent chromium, and therefore has a low impact on the environment.

  The entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2015-240170 and Japanese Patent Application No. 2015-240171 filed on December 9, 2015 are cited herein. However, it is incorporated as the disclosure of the specification of the present invention.

Claims (18)

  A herbicidal material comprising calcium aluminate and soil.   The herbicidal material according to claim 1, further comprising cement.   Furthermore, the herbicidal material according to claim 1 or 2, comprising gypsum. Calcium aluminate, a CaO / _Al 2 _{O 3} molar ratio 1.0 to 3.0, and weed according to claim 1, the content of impurities is not more than 15 wt% Wood. Blaine specific surface area of the calcium aluminate, weed material according to claim 1 is 3000 cm ² / g or more. The vitrification rate of the calcium aluminate calculated | required by a following formula is 70% or more, The herbicidal material of any one of Claims 1-5.
Vitrification rate (%) = 100 × (1-S / S ₀ )
(In the formula, S is a main peak area by powder X-ray diffraction method, and S ₀ is powder X-ray diffraction after heating at 100 ° C. for 2 hours and cooling at a rate of (1 to 10 ° C.) / Min. Main peak area by law.)   The herbicidal material according to any one of claims 1 to 6, wherein the cement content is 100 to 40000 parts by mass with respect to 100 parts by mass of calcium aluminate.   The herbicidal material according to any one of claims 1 to 7, wherein the content of gypsum is 50 to 250 parts by mass with respect to 100 parts by mass of calcium aluminate.   Furthermore, the herbicide of any one of Claims 1-8 containing a calcium silicate. Anti-weed material according to claim 9 calcium silicate, a γ-2CaO · SiO _2.   The herbicidal material according to claim 9 or 10, wherein the content of calcium silicate is 10 to 60 parts by mass with respect to 100 parts by mass in total of calcium aluminate and gypsum.   Furthermore, the herbicidal material according to any one of claims 1 to 11, further comprising a shrinkage reducing agent.   The herbicidal material according to claim 12, wherein the content of the shrinkage reducing agent is 0.5 to 20 parts by mass with respect to 100 parts by mass in total of calcium aluminate and gypsum.   Furthermore, the weed proof material of any one of Claims 1-13 containing a fiber.   The herbicidal material according to claim 14, wherein the fiber content is 0.05 to 5 parts by mass with respect to 100 parts by mass in total of calcium aluminate and gypsum.   A method for using a herbicidal material, wherein the herbicidal material according to any one of claims 1 to 15 is spread on the ground and sprayed onto the ground.   A method for using a herbicidal material, wherein the herbicidal material according to any one of claims 1 to 15 is kneaded with water and spread over the ground to cover the ground.   The usage-amount of the herbicidal material of Claim 16 or 17 whose usage-amount of water is 5-100 mass parts with respect to 100 mass parts of herbicidal materials.