Whitening agent composition for hydraulic composition

Abstract

To provide a whitening agent composition for a hydraulic composition effectively promoting the whitening of a hydraulic composition surface, and a method for producing the hardened body using the same.SOLUTION: A whitening agent composition for a hydraulic composition comprises (A) primary amine having an 8 or more to 22 or less of alkyl group or alkenyl group.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a whitening agent composition for hydraulic compositions and a method for producing a hardened product of a hydraulic composition using the same. [Background technology]

[0002] Hydraulic compositions such as concrete and mortar are mixtures of cement, water, aggregate, and organic materials such as cement dispersants, and harden through a chemical reaction called the hydration reaction of cement to provide robust structures. When cement reacts with water during the hydration reaction, it produces calcium hydroxide, which reacts with carbon dioxide in the air to produce calcium carbonate, which is white in color, and its exposure on the surface of a hydraulic composition is called efflorescence. Efflorescence is also caused by the deterioration of concrete over time, so it reminds the viewer of the passage of time and adds design value to the concrete structure, which is why it is sometimes used in the design of hydraulic compositions.

[0003] For example, Patent Document 1 discloses a method for patterning a cement product, which is characterized by controlling the color of the surface of the cement product by adjusting the degree of calcium efflorescence that precipitates on the surface of the cement product, and thereby forming a pattern. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2000-247765 A DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]

[0005] As a method for promoting efflorescence, a special curing method is known that adjusts the atmosphere during curing of the hydraulic composition. However, this requires additional installation of auxiliary equipment, is affected by the quality of the cement, and can result in unevenness in the degree of whitening.

[0006] The present invention provides a whitening agent composition for hydraulic compositions that effectively promotes whitening of the surface of a hydraulic composition, and a method for producing a hardened product of the hydraulic composition using the same. [Means for solving the problem]

[0007] The present invention relates to a whitening agent composition for hydraulic compositions, which contains (A) a primary amine having an alkyl or alkenyl group having 8 or more and 22 or less carbon atoms.

[0008] The present invention also relates to a method for producing a hardened product of a hydraulic composition, comprising the following steps 1 to 4: Step 1: A step of kneading water and hydraulic powder to obtain a hydraulic composition. Step 2: A step of filling the hydraulic composition obtained in step 1 into a formwork to which the whitening agent composition for hydraulic compositions of the present invention has been applied or sprayed. Step 3: A step of hardening the hydraulic composition filled in the form obtained in step 2. Step 4: A step of removing the hardened body obtained in step 3 from the formwork. Effect of the Invention

[0009] According to the present invention, there are provided a whitening agent composition for hydraulic compositions which effectively promotes whitening of the surface of a hydraulic composition, and a method for producing a hardened product of a hydraulic composition using the same. In recent years, the SDGs "Sustainable Development Goals" have been proposed to realize a sustainable society. The hydraulic composition whitening agent composition of the present invention and the method for producing a hardened hydraulic composition using the same provide a hydraulic composition with excellent designability by whitening the surface, and are therefore considered to be technologies that contribute to, for example, SDGs No. 8, 9, and 11. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The present inventors have found that by using the component (A), which is a primary amine having an alkyl or alkenyl group with a specific number of carbon atoms, a hydraulic composition cured product having excellent surface whiteness can be obtained. The mechanism by which the whiteness of the surface of the hydraulic composition hardened product of the present invention is improved is not entirely clear, but is presumed to be as follows. Alkanolamines are known as agents with carbon dioxide exchange capacity, because their amino groups react with carbon dioxide to form carbonates, enabling the control of carbon dioxide release and absorption by heating and cooling. However, because alkanolamines have high hydrophilicity and metal ion chelating capacity, when used in hydraulic compositions, they dissolve in the bulk water in the hydraulic composition, and are oriented toward the metal ions derived from cement in the bulk water, decreasing the carbon dioxide exchange capacity. This is presumably why they cannot promote the reaction between carbon dioxide in the air and calcium hydroxide in the hydraulic composition, and therefore cannot promote the whitening of the hydraulic composition surface. In the present invention, by using a primary amine having an alkyl or alkenyl group with a specific carbon number as component (A), which has little steric hindrance of the amino group that reacts with carbon dioxide and has appropriate hydrophobicity, the amine maintains its reactivity with carbon dioxide and acts as an assistant in the reaction between carbon dioxide in the air and calcium hydroxide in the hydraulic composition, which is considered to effectively promote the whitening of the surface of the hydraulic composition.

[0011] [Whitening agent composition for hydraulic composition] <Component (A)> The whitening agent composition for hydraulic compositions of the present invention contains, as component (A), a primary amine having an alkyl or alkenyl group having 8 to 22 carbon atoms. The number of carbon atoms in the alkyl or alkenyl group is 8 or more, preferably 10 or more, from the viewpoint of hydrophobicity, and 22 or less, preferably 20 or less, more preferably 18 or less, from the viewpoint of whitening ability.

[0012] Specific examples of component (A) include one or more selected from oleylamine, laurylamine, stearylamine, cocoalkylamine, myristylamine, palmitylamine, and decylamine. From the viewpoint of whitening ability, the component (A) is preferably one or more selected from oleylamine, stearylamine, cocoalkylamine, and laurylamine, and more preferably one or more selected from oleylamine and cocoalkylamine.

[0013] <Composition, etc.> The whitening agent composition for hydraulic compositions of the present invention contains, from the viewpoint of promoting whitening, preferably 5% by mass or more of the component (A), more preferably 10% by mass or more, even more preferably 15% by mass or more, still more preferably 20% by mass or more, still more preferably 25% by mass or more, still more preferably 30% by mass or more, still more preferably 35% by mass or more, and still more preferably 40% by mass or more, and from the viewpoint of releasability, preferably 100% by mass or less, more preferably 80% by mass or less, and still more preferably 60% by mass or less.

[0014] From the viewpoint of releasability, the whitening agent composition for hydraulic compositions of the present invention may optionally contain an oil component as component (B). Examples of component (B) include one or more selected from the group consisting of (1) mineral oils such as kerosene, diesel, spin oil, transformer oil, and machine oil; (2) synthetic oils such as polyalkylene glycol; (3) vegetable oils such as rapeseed, coconut, palm, and soybean oil; (4) fats and oils; and (5) fatty acid esters. From the viewpoint of releasability, component (B) is preferably a mineral oil, more preferably one or more mineral oils selected from kerosene, light oil, spin oil, transformer oil, and machine oil, and even more preferably one or more mineral oils selected from spin oil and machine oil.

[0015] As the component (B), a commercially available product can be used. When a spin oil is used as the component (B), examples of the spin oil include Cosmo Pure Spin E and Cosmo Pure Spin ESP (both manufactured by Cosmo Oil Lubricants Co., Ltd.), with Cosmo Pure Spin ESP being preferred. When machine oil is used as component (B), examples of the machine oil include Cosmo Pure Safety 10, Cosmo Pure Safety 22, Cosmo Pure Safety 32, Cosmo Pure Safety 46, and Cosmo Pure Safety 68 (all manufactured by Cosmo Oil Lubricants Co., Ltd.).

[0016] The whitening agent composition for hydraulic compositions of the present invention contains the (B) component in an amount of preferably 0 mass % or more, more preferably 20 mass % or more, and even more preferably 40 mass % or more from the viewpoint of releasability, and in an amount of preferably 90 mass % or less, more preferably 85 mass % or less, even more preferably 80 mass % or less, still more preferably 75 mass % or less, still more preferably 70 mass % or less, still more preferably 65 mass % or less, and even more preferably 60 mass % or less from the viewpoint of promoting whitening.

[0017] In the whitening agent composition for hydraulic compositions of the present invention, the mass ratio (B) / (A) of the content of the (A) component to the content of the (B) component is preferably 0 or more, more preferably 1 or more, and even more preferably 2 or more from the viewpoint of releasability, and is preferably 19 or less, more preferably 15 or less, even more preferably 10 or less, still more preferably 8 or less, still more preferably 6 or less, and even more preferably 4 or less from the viewpoint of whitening promotion.

[0018] The whitening agent composition for hydraulic compositions of the present invention may contain a surfactant other than the component (A), but the content is limited so as not to impair the effects of the present invention. In the whitening agent composition for hydraulic composition of the present invention, the mass ratio of the content of the (A) component to the content of all surfactants [(A) / total surfactants] is, from the viewpoint of not impairing the effects of the present invention, preferably 70 mass% or more, more preferably 80 mass% or more, even more preferably 90 mass% or more, still more preferably 95 mass% or more, and 100 mass% or less, and may be 100 mass%.

[0019] The whitening agent composition for hydraulic compositions of the present invention may contain a nonionic surfactant other than the component (A), but the content is limited so as not to impair the effects of the present invention. In the whitening agent composition for hydraulic compositions of the present invention, the mass ratio of the content of the (A) component to the content of all nonionic surfactants [(A) / total nonionic surfactants] is, from the viewpoint of not impairing the effects of the present invention, preferably 70 mass% or more, more preferably 80 mass% or more, even more preferably 90 mass% or more, still more preferably 95 mass% or more, and may be 100 mass% or less.

[0020] The whitening agent composition for hydraulic compositions of the present invention may contain, as other components, a defoamer, an antioxidant, a preservative, a metal sealant, and a solvent (excluding the components (A) and (B)).

[0021] The whitening agent composition for hydraulic compositions of the present invention may be used by applying or spraying it onto the surface of a hydraulic composition slurry, or may be used as a form release agent for hydraulic compositions by applying or spraying it onto a form, and is preferably used as a form release agent for hydraulic compositions. The whitening agent composition for hydraulic composition of the present invention may be applied to the surface of the hydraulic composition slurry or a form by spraying, in addition to application with a brush or a mop. The amount of the whitening agent composition for hydraulic compositions of the present invention applied or sprayed onto the surface of a hydraulic composition slurry or a form is preferably 0.5 g / m from the viewpoints of releasability and surface aesthetics. 2 More preferably, 1 g / m 2 More preferably, 1.5 g / m 2 More than 40 g / m 2 Less than 38g / m 2 More preferably 36 g / m or less 2 The following is the result.

[0022] The whitening agent composition for hydraulic compositions of the present invention is intended for hydraulic compositions, more particularly, for mortar compositions or concrete compositions.

[0023] The hydraulic composition contains hydraulic powder. The hydraulic powder is a powder having the physical property of being hardened by a hydration reaction, and examples of the hydraulic powder include cement, gypsum, and the like. Examples of cement include ordinary Portland cement, early strength Portland cement, ultra-early strength Portland cement, sulfate-resistant Portland cement, low-heat Portland cement, white Portland cement, and ecocement (e.g., JIS R5214, etc.). Among these, a cement selected from ordinary Portland cement, sulfate-resistant Portland cement, and white Portland cement is preferred, and ordinary Portland cement is more preferred.

[0024] The hydraulic powder such as cement may contain powder having pozzolanic action and / or latent hydraulic properties such as blast furnace slag, fly ash, silica fume, etc., stone powder (calcium carbonate powder), etc. For example, blast furnace slag cement, fly ash cement, silica fume cement, etc. may be used.

[0025] From the viewpoints of productivity and strength, the hydraulic composition may have a water / hydraulic powder ratio (mass ratio of water to hydraulic powder in the slurry (mass of water / mass of hydraulic powder×100), usually abbreviated as W / P) of preferably 10% or more, more preferably 15% or more, even more preferably 20% or more, still more preferably 30% or more, and preferably 60% or less, more preferably 55% or less, and even more preferably 50% or less.

[0026] The hydraulic composition may further contain aggregate. Examples of aggregate include fine aggregate and coarse aggregate, and the fine aggregate is preferably mountain sand, land sand, river sand, or crushed sand, and the coarse aggregate is preferably mountain gravel, land gravel, river gravel, or crushed stone. Depending on the application, lightweight aggregate may be used. The term aggregate is based on "Concrete Overview" (published by Gijutsu Shoin on June 10, 1998).

[0027] The aggregate may be used in the usual range used in preparing concrete, mortar, etc. When the hydraulic composition is concrete, the amount of coarse aggregate used is preferably 50% or more by bulk volume, more preferably 55% or more, even more preferably 60% or more, and preferably 100% or less, more preferably 90% or less, even more preferably 80% or less, from the viewpoint of the properties of the concrete. Also, when the hydraulic composition is concrete, the amount of fine aggregate used is 500 kg / m or less from the viewpoint of improving the filling property into a formwork, etc. 3 More than 600kg / m is preferable. 3 More preferably, 700 kg / m 3 More preferably, 1000 kg / m 3 Less than 900kg / m is preferable. 3 The following is more preferable: When the hydraulic composition is mortar, the amount of fine aggregate used is 800 kg / m 3 More than 900kg / m is preferable. 3 More preferably, 1000kg / m 3 More preferably, 2000 kg / m 3 Less than 1800kg / m is preferable. 3 Less than 1700kg / m is more preferable. 3 The following is even more preferred:

[0028] The hydraulic composition may further contain other components in addition to the above components. Examples of the components include dispersants, defoamers, AE agents, retarders, foaming agents, thickeners, foaming agents, waterproofing agents, fluidizing agents, and early strength agents. Examples of the early strength agents include compounds selected from hydrochlorides, sulfates, nitrates, nitrites, cyanates, thiocyanates, thiosulfates, and formates of alkali metals and alkaline earth metals, organic compounds selected from alkanolamines, glycerin derivatives, formaldehyde derivatives, and catechol derivatives, and nanoparticles of Portland cement hydration products (CSH, and calcium hydroxide).

[0029] [Method for producing whitening agent composition for hydraulic composition] The method for producing a whitening agent composition for hydraulic compositions of the present invention is a method for producing the whitening agent composition for hydraulic compositions, which comprises mixing component (A) and, optionally, component (B). The method for producing the whitening agent composition for hydraulic compositions of the present invention can appropriately apply the matters described for the whitening agent composition for hydraulic compositions of the present invention. The components (A), (B) and other components are the same as those described in the whitening agent composition for hydraulic compositions of the present invention. In the manufacturing method of the whitening agent composition for hydraulic composition of the present invention, the mixing amount and mass ratio of each component can be applied by replacing the content and mass ratio of each component described in the whitening agent composition for hydraulic composition of the present invention with the mixing amount.

[0030] [Method for producing a hardened product of a hydraulic composition] The method for producing a hardened product of a hydraulic composition of the present invention includes the following steps 1 to 4. Step 1: A step of kneading water and hydraulic powder to obtain a hydraulic composition. Step 2: A step of filling the hydraulic composition obtained in step 1 into a formwork to which the whitening agent composition for hydraulic compositions of the present invention has been applied or sprayed. Step 3: A step of hardening the hydraulic composition filled in the form obtained in step 2. Step 4: A step of removing the hardened body obtained in step 3 from the formwork. The matters described in relation to the whitening agent composition for hydraulic compositions of the present invention and its production method can be appropriately applied to the production method of the hardened product of the hydraulic composition of the present invention.

[0031] In step 1, the embodiments described in the hydraulic composition can be appropriately applied. In step 1, the contents of each component in the hydraulic composition can be read as mixture amounts.

[0032] In step 2, the whitening agent composition for hydraulic compositions of the present invention may be applied to the formwork by spraying with a sprayer, in addition to application with a brush or a mop. These release agents can also be used as lubricants. The amount of the whitening agent composition for hydraulic compositions of the present invention applied or sprayed onto a formwork is preferably 0.5 g / m from the viewpoints of releasability and surface appearance. 2 More preferably, 1 g / m 2 More preferably, 1.5 g / m 2 More than 40 g / m 2 Less than 38g / m 2 More preferably 36 g / m 2 The following is the result. The method of filling the hydraulic composition into the formwork may include a method of directly charging the hydraulic composition from a mixer, a method of feeding the hydraulic composition with a pump and introducing it into the formwork, and the like.

[0033] In step 3, the hydraulic composition filled in the form obtained in step 2 is hardened. In step 3, for example, the curing conditions are such that the time during which the hydraulic composition is held at a curing temperature of 50° C. or higher is preferably 1 hour or longer, and preferably 24 hours or shorter, and more preferably 20 hours or shorter. When the hydraulic composition filled in the formwork is held at 50° C. or higher for curing, the curing can be performed by autoclave curing or heating with steam or the like. In step 3, the hydraulic composition may be hardened without steam curing. When producing a mortar or concrete product without steam curing, the time from contacting the cement with water in the preparation of the hydraulic composition to demolding is preferably 4 hours or more and 48 hours or less from the viewpoints of productivity and strength. In this case, the temperature is preferably 0°C or more, more preferably 5°C or more, and 45°C or less, more preferably 40°C or less. Heating and / or cooling within this temperature range can be performed as appropriate.

[0034] In step 4, the hardened body obtained in step 3 is demolded from the mold. Steps 3 and 4 can be carried out consecutively under a series of temperature control. The hardened body can be demolded according to a known method. In the present invention, the time from the start of preparation of the hydraulic composition to demolding, i.e., the time from contacting the cement with water to the start of demolding, is preferably 4 hours or more, more preferably 5 hours or more, and is preferably 48 hours or less, more preferably 40 hours or less, from the viewpoints of productivity and strength.

[0035] The hardened hydraulic composition obtained by the method for producing a hardened hydraulic composition of the present invention is suitable for use in high-fluidity concrete, underwater non-segregation concrete, lightweight high-fluidity concrete, permeable concrete, cast-in-place lining method (ECL method), and SENS method. EXAMPLES

[0036] The following components (A) and (B) were used.

[0037] <Component (A)> a-1: Farmin OV, oleylamine, manufactured by Kao Corporation a-2: Farmin 20D, laurylamine, manufactured by Kao Corporation a-3: Stearylamine, manufactured by Tokyo Chemical Industry Co., Ltd. a-4: Farmin CS, cocoalkylamine, manufactured by Kao Corporation

[0038] <Component (A') (comparison component for component (A))> a'-1: Hexylamine, Fujifilm Wako Pure Chemical Industries, Ltd. a'-2: Farmin DM2098, lauryl dimethylamine, manufactured by Kao Corporation a'-3: Triethanolamine, manufactured by Tokyo Chemical Industry Co., Ltd.

[0039] <(B) component> b-1: Cosmo Pure Safety 68, manufactured by Cosmo Oil Lubricants Co., Ltd. b-2: Cosmo Pure Spin E, manufactured by Cosmo Oil Lubricants Co., Ltd.

[0040] (1) Method for preparing whitening agent composition for hydraulic composition The above components were added to a 50 mL vial so as to have the contents shown in Table 1, and mixed vigorously by inversion at 20° C. to prepare each whitening agent composition for hydraulic compositions.

[0041] (2) Adjustment of formwork Each whitening agent composition for hydraulic composition prepared by the method described in (1) was applied to a cylindrical steel formwork (height 10 cm, inner diameter 5 cm) using a brush.

[0042] (3) Preparation of Uncured Curable Composition Mortar was prepared according to the composition shown in Table 2. The mortar was prepared by adding an aqueous solution of water and cement dispersant to a mixture of cement and sand, and kneading for 120 seconds at 62 rpm using a mortar mixer specified in JIS R5201. As the cement dispersant, MIGHTY 21VS (manufactured by Kao Corporation) was used, and the amount of cement dispersant added was adjusted to 250±10 mm using a flow cone (upper diameter 70 mm × lower diameter 100 mm × height 60 mm) specified in JIS R 5201, and the effective solid content mass part was 0.13 mass parts relative to the powder in all examples and comparative examples.

[0043] The ingredients used in preparing the mortar were as follows: Cement: A 1:1 (by mass) mixture of ordinary Portland cement manufactured by Taiheiyo Cement Co., Ltd. and ordinary Portland cement manufactured by Sumitomo Osaka Cement Co., Ltd., specific gravity 3.16 Sand: Joyo, Kyoto Prefecture Surface dry specific gravity 2.50 Water: Tap water (The water content in Table 2 includes the cement dispersant)

[0044] (4) Preparation of hardened body The unhardened mortar prepared by the method described in (3) was filled into a cylindrical steel formwork (height 10 cm, inner diameter 5 cm) coated with the whitening agent composition for hydraulic compositions prepared by the method described in (2) in 5 seconds, hardened for 15 hours by curing in air at 20°C, and then demolded.

[0045] (5) Evaluation of whiteness The hardened mortar body prepared by the method described in (5) was removed from the cylindrical steel formwork (height 10 cm, inner diameter 5 cm), and the surface of the hardened body after removal from the formwork was photographed with a digital camera. The obtained image was then subjected to histogram analysis using the open source software ImageJ, and the median and mode of 256 levels from black (0) to white (255) were calculated and used as an index of whiteness. The results are shown in Table 1. It can be said that the higher the median and mode values, the higher the whiteness. The results are shown in Table 1.

[0046] [Table 1]

[0047] [Table 2]

[0048] In Table 1, Examples 1 to 8 showed higher median and mode values ​​of whiteness than Comparative Examples 1 to 5. This is believed to be because the whitening agent composition for hydraulic compositions of the present invention contains component (A), which is a primary amine with less steric hindrance of the amino group that reacts with carbon dioxide and has appropriate hydrophobicity, and the amine acts as an assistant in the reaction between carbon dioxide in the air and calcium hydroxide in the hydraulic composition on the surface of the hydraulic composition, effectively promoting the whitening of the hydraulic composition surface.

Claims

1. The composition comprises (A) a primary amine having a linear alkyl or alkenyl group having from 8 to 22 carbon atoms (hereinafter referred to as component (A)), and optionally (B) an oil component (hereinafter referred to as component (B)), the mass ratio (B) / (A) of the content of the (A) component to the content of the (B) component is 0 or more and 9 or less; Whitening agent composition for hydraulic compositions.

2. The whitening agent composition for hydraulic compositions according to claim 1, which is used by applying or spraying onto the surface of the hydraulic composition.

3. The whitening agent composition for hydraulic compositions according to claim 1 or 2, which is used as a form release agent for hydraulic compositions.

4. The whitening agent composition for hydraulic compositions according to any one of claims 1 to 3, comprising 5 mass% or more and 100 weight% or less of the component (A).

5. The whitening agent composition for hydraulic compositions according to any one of claims 1 to 4, wherein the component (B) is one or more mineral oils selected from kerosene, light oil, spin oil, transformer oil, and machine oil.

6. A method for producing a hardened product of a hydraulic composition having a whitened surface, comprising the following steps 1 to 4: Step 1: A step of kneading water and hydraulic powder to obtain a hydraulic composition. Step 2: A step of filling the hydraulic composition obtained in step 1 into a formwork to which the whitening agent composition for hydraulic compositions according to any one of claims 1 to 5 has been applied or sprayed. Step 3: A step of hardening the hydraulic composition filled in the form obtained in step 2. Step 4: A step of removing the hardened body obtained in step 3 from the mold.

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