JPH1036155A - Powdery or granular material for retarding hardening of cement and production of concrete structure using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a powdery or a granular material for retarding the hardening of a cement capable of simply and efficiently forming an aggregate exposed finish surface by washing on the surface of a concrete structure. SOLUTION: This powdery or granular material 2 for retarding the hardening of a cement comprises a powdery or a granular substrate and a covering material for covering the surface of the powdery or granular substrate. The covering material contains a component for retarding the hardening of the cement. A polymer, etc., capable of manifesting the ability to retard the hardening of the cement by hydrolysis can be used as the component for retarding the hardening of the cement. The polymer includes an unsaturated polyester, etc., prepared by reacting a polyvalent carboxylic acid component such as maleic acid with a polyol component such as ethylene glycol. The powdery or granular substrate includes a powdery or a granular metal, powdery or granular ceramics, an inorganic molding product, a resin molding product, etc. The powdery or granular material 2 for retarding the hardening of the cement is brought into contact with a surface of an inorganic hardenable composition 4 to carry out the hardening treatment of the inorganic hardenable composition 4. The powdery or granular material 2 for retarding the hardening of the cement and the unhardened inorganic hardenable composition 4 can be removed to thereby form an aggregate exposed finish surface by washing having a natural feeling on the surface of a concrete structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface-decorated concrete product having a pattern or decoration on its surface, or a concrete-paved road having a rough surface for preventing slippage or the like. The present invention relates to a cement granulation delay granule useful for producing a formed concrete structure, and a method for producing a concrete structure using the same.

[0002]

2. Description of the Related Art It is often practiced to decorate the surfaces of concrete moldings and various buildings using a washing method, which is one of plastering techniques. This washing-out method is a method in which a portion of the aggregate is exposed by rinsing the mortar of the concrete surface layer by washing with water immediately before the cement hardens. This method
Since the curing speed of concrete is closely related, the timing of washing out is limited to a very narrow range in time, which is not a technique suitable for mass production or application to large buildings.

[0003] In addition, a method of using a unit tile in which a plurality of tiles are adhered and arranged on the surface of an adhesive layer of an adhesive tape has been proposed for applying a tile to a concrete surface. In the method using this unit tile,
Place the unit tile on the formwork where concrete is poured, pour the mortar into the formwork, cure, then remove the mold,
After exposing the tile on the surface by removing the adhesive sheet, the tile is constructed by removing the hardened cement by going around the tile surface and finishing the surface. This surface finishing is often an indispensable step in the construction of a tile characterized by its clean surface, in which the hardened cement adhered to the tile is often manually scraped off.
However, the operation of removing the hardened cement adhered to the tile is time-consuming and troublesome and complicated, and not only increases the tile construction cost, but also causes the tile surface to be damaged by the hardened cement removing operation.

In addition, natural stone, crushed stone,
There is also a need for concrete products decorated with decorative materials such as glassware, pottery, and metal products. However, such concrete products often have irregular shapes and are complicated, so there is no appropriate padding, and the
It takes an extremely long time to remove the waste.

In order to solve such problems, it has been proposed to apply a cement setting retarder to inhibit the hardening of only the surface layer of concrete, to process the surface of a concrete product, or to form a pattern on the surface. Have been.

Japanese Patent Application Laid-Open No. Hei 3-224953 discloses that decorative materials such as tiles and stones are arranged on a bottom plate of a mold via an injected embedding agent (concrete non-hardening agent), and concrete is cast. A method for manufacturing a concrete block integrated with a decorative material by removing the mold after curing and removing the embedding agent from the surface of the concrete product by washing with water is disclosed.

Japanese Unexamined Patent Publication No. Hei 3-175003 discloses that a decorative material is temporarily attached to the inner surface of a mold via an uncured coating material layer, and concrete is cast and cured, and then removed from the concrete product. A method for manufacturing a concrete product having a decorative surface by removing the uncured coating material on the surface of the concrete and the uncured portion of the concrete by washing with water.

However, in these methods, it is necessary to inject a non-curing agent or a non-curing coating agent, or to apply the non-curing coating agent to the surface of the decorative material, thereby improving workability and productivity of concrete products. It is difficult.

[0009] The concrete washing flat plate is used for backing after a mortar composition is poured into a mold on which a cement setting retarder is applied or a mold on which paper impregnated with the cement setting retarder is laid. The mortar composition is cast and cured, and after the mortar composition has hardened, it is released from the mold and the concrete surface to which the hardening retarder has adhered is washed.

JP-A-5-38711 and JP-A-5-87711
No. 50411 discloses that a mixture containing a super retarder, a tackifier, a bulking agent and a white pigment is adhered to the inner surface of a mold,
Place mortar or concrete, cure and demold,
There is disclosed a method of washing out a cement paste on a contact surface of a cement product with a mold and finishing the surface of the cement product.

[0011] In addition, as a method of forming an uneven pattern on the surface of a concrete product, a method using a cement setting retarder and a method using a paper pattern impregnated or coated with the cement setting retarder are known. For example, JP-A-63
Japanese Patent No. 216703 discloses a process of cutting a paper pattern impregnated with a curing retarder into a paper to produce a paper cutting pattern corresponding to a pattern such as a predetermined character or figure, and bonding the paper cutting pattern to a predetermined portion of the inner surface of the formwork. Through a process, a step of pouring and curing the mortar composition in the form, a step of disassembling the form and taking out the concrete product, and a step of washing the pattern portion of the concrete product, Is formed. JP-A-61-2028
No. 03 discloses a method in which a tile or the like is attached to paper coated with a cement setting retarder, set in a mold, and washed out in the same manner as described above.

In the method using a cement setting retarder in place of the pattern paper, a step of drawing a predetermined pattern on the form using the setting retarder, a step of pouring mortar and taking out from the form in the same manner as described above; The pattern is formed by a step of cleaning the uncured surface corresponding to the portion where the pattern is formed.

However, the pattern paper impregnated or coated with the cement setting retarder has a low strength against the mortar composition being cast, so that the pattern paper is torn or misaligned with the formwork, so that a predetermined part of the concrete product is not formed. It is difficult to form a washout surface and a pattern on the surface.

The conventional setting retarder for suppressing the hydration mechanism of cement has high solubility in water,
Dissolves in water in cement concrete. Therefore, the hardening retarder dissolves with the mortar or concrete, and flows with excess bleed water in the mortar or concrete in the formwork or on the surface of the molded article or structure. Therefore, while the curing retarder flows to the places where washing is unnecessary, the curing retarder is locally concentrated,
The curing retarder flows out in the area where washing and decoration are required. In addition, on the surface through which the bleeding water has passed, the washing depth is particularly deep. Therefore, it may be difficult to accurately form particularly complicated decorations, such as decorative characters and figures, on predetermined portions of the surface of a concrete molded product or a building.

Further, in order to form a graphic pattern, it is necessary to cut the pattern into a predetermined shape and size, and fix the pattern to the form with an adhesive. Therefore, it is difficult to form a complicated wash surface and pattern, and when forming a pattern on a large number of concrete products, the work is complicated,
Decrease productivity of concrete products. On the other hand, when a cement setting retarder is directly applied to a mold, it takes time to dry and harden the setting retarder, which not only reduces the productivity but also makes it difficult to apply the cement setting agent uniformly. The thickness of the hardening retardation layer varies, making it difficult to form a uniform washout surface or pattern on the surface of the concrete product.

On the other hand, on a concrete pavement road, in order to prevent slippage, an irregularity is formed on the road surface by partially embedding a ring-shaped stone plate or the like in the road. However, according to this method, it is necessary to individually embed the slabs, so that the working efficiency is extremely low.

[0017]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a cement setting retarding powder which can easily and efficiently form a washout surface on the surface of a concrete structure. Another object of the present invention is to suppress the occurrence of breakage or misalignment even when the mortar composition is cast, and to uniformly suppress hardening at the contact surface with the mortar composition, and An object of the present invention is to provide a cement hardening retarding powder which can form a washout surface at a predetermined portion of the surface of the cement with high accuracy. Still another object of the present invention is to provide
It is an object of the present invention to provide a cement hardening delay powder which is useful for obtaining a concrete structure whose surface is decorated with a decorative material or the like. Another object of the present invention is that even a decorative material having a complicated shape can be easily fixed to the surface of a concrete structure,
It is an object of the present invention to provide a powder for granulation for delaying cement setting, which can enhance the decorative property.

Still another object of the present invention is to provide a method for easily and efficiently producing a concrete structure having a washed surface formed on its surface. Still another object of the present invention is to provide a method of manufacturing a concrete structure whose surface can be easily decorated with a decorative material while suppressing damage. It is another object of the present invention to provide a method for manufacturing a concrete structure in which a predetermined pattern is accurately formed at a predetermined portion. Still another object of the present invention is to provide a method for easily manufacturing a concrete structure having a surface having a non-slip effect.

[0019]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that the surface of a granular substrate is coated with a coating containing a cement setting retarding component. It has been found that when used, it is possible to uniformly suppress hardening at the contact surface with the mortar composition, and to remove the hardened mortar composition after hardening, so that a beautiful washout surface can be easily formed on the surface of the concrete structure. Completed the invention.

That is, the present invention is directed to a cement setting retarder comprising a powdery or granular substrate and a coating covering the surface of the powdery or granular substrate, wherein the coating comprises a cement setting retarding component. Provide a powder. As the cement setting delay component, a polymer capable of exhibiting cement setting delay ability by hydrolysis, a cement setting delay agent, or the like can be used.

The polymer includes unsaturated polyester,
For example, unsaturated polyester obtained by reacting a polyvalent carboxylic acid component such as maleic acid, maleic anhydride, fumaric acid or a derivative thereof with a polyol component such as ethylene glycol, propylene glycol, glycerin or a condensate thereof. Is included. The unsaturated polyester may be a cured product by crosslinking.

The cement setting retarder includes phosphoric acid or a salt thereof, boric acid or a salt thereof, hexafluorosilicate,
Examples include phosphonic acids, oxycarboxylic acids, keto acids, polyhydric phenols, ligninsulfonic acids, saccharides and the like. Further, as the granular substrate, for example, a granular metal, a granular ceramic, an inorganic molded product, a resin molded product, or the like can be used.

The present invention also relates to a method for producing a concrete structure having a scouring surface formed on the surface thereof, wherein the powder for cement setting retardation is brought into contact with the surface of the inorganic curable composition, and the inorganic setting is performed. The present invention provides a method for producing a concrete structure, which comprises removing a cement setting delay powder and an uncured inorganic curable composition after curing a curable composition. The particles for delaying cement setting may be removed by suction.

In the present specification, unless otherwise specified, the term “granular” is used to mean not only powdery and granular, but also broadly, such as gravels, blocks and the like. The term "body" includes not only powders and granules but also clumps such as gravel, blocks, and moldings. The term “cement” refers to an inorganic substance that shows curability when mixed with water, and is used to include air-hardened cement, hydraulic cement, and the like. Furthermore, the curable composition containing cement includes a cement paste, a mortar composition, and a concrete composition, and these may be simply referred to as “inorganic curable composition”. “Concrete structure (product)” means a structure (product) obtained by curing an inorganic curable composition. The “polycarboxylic acid derivative” refers to a polycarboxylic acid anhydride, a polycarboxylic acid lower alkyl ester (for example, a removable C _1-4 alkyl ester such as a methyl ester or an ethyl ester). Used to include the meaning.

[0025]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to the drawings as necessary. In the drawings, the same members and elements are denoted by the same reference numerals.

The cement / curing retarding powder of the present invention comprises a powdery / granular substrate and a cement setting / retarding component covering the surface of the powdery / granular substrate.

The powdery or granular substrate only needs to have such a strength that it can maintain its own shape even when it comes into contact with the inorganic curable composition, and it is insoluble or hardly soluble in water. preferable. The substrate may be made of any of an inorganic material and an organic material, and may be any of a natural product and a processed product. Processed products include crushed products, crushed products, and molded products.

The inorganic materials include, for example, metals, ceramics and the like. Examples of the metal include iron and aluminum, and alloys containing these metals. Ceramics include metal or non-metallic compounds,
Or a wide range of solid inorganic materials used in the ceramics industry, such as mixtures thereof, such as clays and minerals (eg, diatomaceous earth, kaolin, talc, bentonite, clay,
Stone powder, volcanic ash, coal ash, etc.), sand, gravel, metal or non-metal oxides or sulfides (eg, silica, alumina, zinc oxide, iron oxide, titanium oxide, molybdenum disulfide, etc.),
Examples thereof include glass, cement, metal salts (eg, carbonates and sulfates of alkaline earth metals such as gypsum (calcium sulfate), calcium carbonate, and barium sulfate), lime, and carbon (carbon black, graphite, and the like). The inorganic materials can be used alone or in combination of two or more.

The processed product made of an inorganic material is obtained by crushing or crushing the inorganic material to an appropriate size by, for example, a conventional crushing means (for example, a ball mill, a vibrating ball mill, a hammer mill, a jet mill, a cutter mill, etc.). And
Classification and granulation as necessary, or molding into a desired shape and size using a conventional tableting machine (for example, press molding machine, granulator, etc.), and drying and firing as necessary Can be obtained. A molded article made of a metal material can be manufactured by subjecting the metal material to a conventional casting method.

The organic materials include wood and resin. The resin is not particularly limited, vinyl chloride resin,
Vinylidene chloride resin, vinyl acetate resin, polystyrene resin, (meth) acrylic resin, olefin resin,
Any of thermoplastic resins such as polyamide, polyacetal, polycarbonate, saturated polyester and cellulose plastic; and thermosetting resins such as phenol resin, urea resin and polyurethane may be used. The organic materials can be used alone or in combination of two or more. The powdery or granular substrate composed of an organic material is used to cut wood, a lump of resin obtained by a conventional polymerization method, or the like, to an appropriate size by a conventional cutting means or pulverizing means, if necessary, Crushed,
It can be obtained by classifying and granulating as required. In addition, the resin may be manufactured by subjecting it to a conventional molding method, for example, compression molding, extrusion molding, injection molding, or the like, molding it into an appropriate shape, and cutting it into a desired size as necessary. it can. In order to adjust the specific gravity, a mixture containing the inorganic material and the organic material in an appropriate ratio may be molded by the molding method.

For inorganic or organic molded articles, if necessary,
Various additives, for example, fillers, binders, stabilizers, plasticizers, defoamers, emulsifiers, hydrolysis accelerators, polymerization inhibitors and the like may be added.

Preferred examples of the granular substrate include granular metal, granular ceramic, inorganic molded products, and resin molded products. In addition, a material having a large specific gravity (for example, a specific gravity of 1 or more,
Preferably, specific gravity is about 1 to 10, more preferably 1.5.
For example, when a granular substrate composed of an inorganic material is used, it is possible to prevent the cement-setting retardation granular material from floating on the bleed water, being washed away, and being blown off by the wind.

The shape and size of the granular substrate can be appropriately selected in accordance with the desired shape and size of the cement setting retarding granular material. For example, the size (average diameter) of the granular substrate is 0.1 μm to 50 cm (for example, 1 μm to 50 cm).
cm, especially about 10 μm to 50 cm), preferably 50 μm to 20 cm, more preferably 100 μm to 5 cm.
cm.

The cement setting retarding component may be any component capable of exhibiting the action of delaying or suppressing the setting of cement, and includes, in addition to the cement setting delaying agent, a polymer capable of exhibiting cement setting delaying ability by hydrolysis. It is.
These components can be used alone or in combination of two or more.

Examples of the cement setting retarder include a setting retarder or a setting retarder for lowering the setting speed of cement, and inorganic or organic setting retarders can be used. Inorganic cure retarders include phosphoric acid, boric acid or salts thereof, hexafluorosilicate, and the like. Organic curing retardants include phosphonic acids, oxycarboxylic acids, polycarboxylic acids, keto acids, polyphenols, sugars, humic acids,
Lignin sulfonic acids, homo- or copolymers of a monomer having a carboxyl group or a salt thereof, and a polymer having a phosphonic acid group are included.

The phosphonic acids include aminodi (methylenephosphonic acid), aminotri (methylenephosphonic acid),
1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid) or a salt thereof (for example, ammonium salt; sodium, potassium) Alkali metal salts such as calcium, magnesium and barium).

The oxycarboxylic acids include glycolic acid, lactic acid, malic acid, tartaric acid, citric acid, gluconic acid,
Oxycarboxylic acids such as gallic acid and 2,4,6-trihydroxybenzoic acid or salts thereof, and lactones corresponding to oxycarboxylic acids such as ascorbic acid and isoascorbic acid. Examples of the polycarboxylic acids include saturated polycarboxylic acids such as oxalic acid, malonic acid, and succinic acid; and unsaturated polycarboxylic acids such as fumaric acid, itaconic acid, and maleic acid. Examples of the keto acids include keto acids such as pyruvic acid and α-ketoglutaric acid, and salts thereof. Examples of polyhydric phenols include pyrogallol. Sugars include polysaccharides such as sucrose, corn syrup, and the like. Examples of lignin sulfonic acids include lignin sulfonic acid and lignosulfonate (for example, calcium lignosulfonate). As a monomer or a copolymer or a salt thereof having a carboxyl group,
Polymaleic acid, polyfumaric acid, styrene-maleic acid copolymer, polyacrylic acid, polymethacrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylate- (meth) acrylic acid copolymer, ethylene Examples thereof include a polymer such as a sulfonic acid-acrylic acid copolymer or a salt thereof (preferably, a low molecular weight polymer or a salt thereof). Among these curing retarders, inorganic curing retarders, phosphonic acids, oxycarboxylic acids, keto acids, polyhydric phenols, sugars, lignin sulfonic acids and the like are preferred. These cement setting retarders can be used alone or in combination of two or more.

Examples of the polymer capable of exhibiting a cement setting delaying ability by hydrolysis include a polymer having a group capable of forming a group having a cement setting delaying ability such as a hydroxyl group or a carboxyl group by hydrolysis, such as polyester. Can be The polymers can be used alone or in combination of two or more.

The polyester can be obtained by a condensation reaction between a carboxylic acid component containing a polyhydric carboxylic acid or a derivative thereof and a polyol component containing a polyhydric alcohol or a condensate thereof.

The polycarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and other saturated polycarboxylic acids having 2 to 6 carbon atoms in the main chain; maleic acid, maleic anhydride, fumaric acid. Acid, itaconic acid, itaconic anhydride,
It includes unsaturated polycarboxylic acids having 4 to 6 carbon atoms in the main chain, such as citraconic acid, citraconic anhydride, and mesaconic acid. The saturated carboxylic acid and the unsaturated carboxylic acid may be used in combination. These polycarboxylic acids can be used alone or in combination of two or more.

The polycarboxylic acid component includes, in addition to the above polycarboxylic acids, aliphatic polycarboxylic acids (eg, azelaic acid, sebacic acid, etc.) and aromatic polycarboxylic acids (eg, phthalic acid, phthalic anhydride). , Terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, etc.). In particular, phthalic acid, terephthalic acid, isophthalic acid or a polyvalent carboxylic acid component containing a derivative thereof selected from isophthalic acid or a derivative thereof, the strength, elongation, flexibility, flexibility of the polyester, It is useful for adjusting properties such as water resistance.

The content of the aromatic polycarboxylic acid in the whole polyester is, for example, 0.1 to 30% by weight, preferably 0.1 to 20% by weight (for example, 1 to 15% by weight),
More preferably, it is 0.1 to 10% by weight (for example, 2 to 10% by weight).
% By weight).

Preferred polycarboxylic acid components include (1)
Polycarboxylic acid component containing an unsaturated aliphatic dicarboxylic acid having 4 to 6 carbon atoms in the main chain or a derivative thereof (particularly, a polycarboxylic acid component containing at least maleic acid, maleic anhydride, fumaric acid, or a derivative thereof) Or (2) an unsaturated aliphatic dicarboxylic acid having 4 to 6 carbon atoms in the main chain or a derivative thereof, and at least one aromatic dicarboxylic acid selected from phthalic acid, terephthalic acid, and isophthalic acid, or a derivative thereof. And a polycarboxylic acid component containing a derivative.

The polyol component includes polyhydric alcohols having 2 to 4 carbon atoms, for example, diols (for example, C _2-4 alkylene glycol such as ethylene glycol, propylene glycol, 1,3-butanediol, tetramethylene glycol), C _2-4 polyoxyalkylene glycol is a condensation product of an alkylene glycol, e.g., dioxyethylene glycol, trioxyethylene grayed reel,
Polyoxyethylene glycol (hereinafter, these may be simply referred to as polyethylene glycol unless otherwise specified), dioxypropylene glycol, trioxypropylene glycol, polyoxypropylene glycol (hereinafter, unless otherwise specified, these are simply referred to as polyethylene glycol). Polypropylene glycol), polyoxytetramethylene glycol, etc .; polyols (eg, glycerin, diglycerin, polyglycerin, etc.)
Is included. These polyol components may be used alone or in combination.

Preferred polyhydric alcohols include ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, dioxyethylene glycol, trioxyethylene glycol, polyoxyethylene glycol, dioxypropylene glycol, trioxypropylene glycol, Includes polyoxypropylene glycol and glycerin. The polyhydric alcohol often contains a polyhydric alcohol component composed of an aliphatic polyhydric alcohol having 2 to 4 carbon atoms (particularly, a diol) or a condensate thereof.

The molecular weight of the polyoxyalkylene glycol is, for example, about 100 to 7,500, preferably about 200 to 5,000 (for example, about 200 to 2,500), and when polyethylene glycol is used, the weight average molecular weight is 300 or less. Often.

The polyhydric alcohol may be used in combination with another polyol, if necessary, for example, trimethylolethane, trimethylolpropane, pentaerythritol and the like.

Among these polyesters, unsaturated polyesters, particularly unsaturated polyesters containing maleic acid or maleic anhydride as a polycarboxylic acid component are preferred.

The molecular weight of the polyester is not particularly limited.
For example, the weight average molecular weight is 300 to 100,000 (for example, 300 to 25,000), preferably 300 to 500.
00 (e.g., 500 to 15000), and more preferably about 500 to 20,000. The molecular weight of the unsaturated polyester is from 300 to 1 weight average molecular weight.
00000, preferably 300 to 50,000, more preferably about 500 to 10000, and often has a weight average molecular weight of 300 to 5000 (for example, 500 to 5000), particularly about 500 to 2500. The molecular weight is
It is a weight average molecular weight in terms of polystyrene determined by gel permeation chromatography.

A polyester such as an unsaturated polyester can be obtained by a conventional method, for example, by condensing a polyhydric carboxylic acid component and a polyhydric alcohol component in the presence of a catalyst. When an unsaturated polycarboxylic acid such as maleic acid or maleic anhydride is used, a condensation reaction is often performed in the presence of a radical polymerization inhibitor such as hydroquinone. The polyester can be selected from a range of about 0.5 to 3 equivalents, preferably about 0.7 to 2 equivalents of the polyhydric alcohol per 1 equivalent of the polyvalent carboxylic acid. A polyester having a small molecular weight is often obtained by excessively using one of the components of a polycarboxylic acid and a polyol.

The unsaturated polyester may be a crosslinked cured product. The cured product of the unsaturated polyester is obtained by curing the polymerizable composition (i) containing the unsaturated polyester and the polymerization initiator. Examples of the polymerization initiator include various organic peroxides such as methyl ethyl ketone peroxide, cumene hydroperoxide, benzoyl peroxide, t-butylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, dicumyl. Peroxide and the like can be used. The amount of the polymerization initiator used is in a range that does not impair the polymerizability, for example, about 0.5 to 5 parts by weight, preferably about 1 to 4 parts by weight, based on 100 parts by weight of the unsaturated polyester, and 2 to 3 parts by weight. Copies in most cases. The cured product of the unsaturated polyester is a polymerizable composition (i) containing an unsaturated polyester, a polymerizable vinyl monomer (a reactive diluent), and the polymerization initiator.
The cured product of i) may be used. Examples of the polymerizable vinyl monomer include styrene, α-methylstyrene,
Styrene monomers such as vinyltoluene, and alkyl (C) alkyl groups such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate
Alkyl (meth) acrylate of about 20 (especially 1 to 10 carbon atoms), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3
-Hydroxypropyl (meth) acrylate, (meth)
Monomers having a functional group (hydroxyl group, carboxyl group, glycidyl group, etc.) such as acrylic acid and glycidyl (meth) acrylate, esters of (meth) acrylic acid with the above polyhydric alcohols (eg, polyethylene glycol) (eg, ethylene glycol Mono (or di) (meth) acrylate, diethylene glycol mono (or di) (meth) acrylate, polyethylene glycol mono (or di) (meth) acrylate, and the like. Examples of the vinyl monomer include vinyl esters such as vinyl acetate, halogen-containing vinyl monomers such as vinyl chloride, vinyl cyanide such as acrylonitrile,
Olefinic monomers such as ethylene and propylene can also be used. These polymerizable monomers can be used alone or in combination of two or more. Preferred polymerizable vinyl monomers include acrylic monomers and methacrylic monomers, especially (meth) acrylic acid glycol esters. The amount of the polymerizable vinyl monomer used is, depending on the molecular weight of the unsaturated polyester, within a range that does not impair the curing retarding ability or the handleability of the unsaturated polyester, for example, 1 to 500 parts by weight based on 100 parts by weight of the unsaturated polyester. Parts (for example, 1 to 100 parts by weight), preferably 5 to 20 parts by weight.
It can be selected from a range of about 0 parts by weight (for example, 5 to 100 parts by weight), and may be a range of about 5 to 30 parts by weight.
The cured product of the unsaturated polyester is a component of the polymerizable composition (that is, an unsaturated polyester and a polymerization initiator constituting the polymerizable composition (i), and a polymerizable composition (i
It may be a cured product of the polymerizable composition (iii) containing a polymerization accelerator in addition to the unsaturated polyester, the polymerizable vinyl monomer and the polymerization initiator constituting i)). The polymerization accelerator, for example, cobalt naphthenate, organic acid cobalt salts such as cobalt octylate, acetylacetone, β-diketone or β-ketoesters such as ethyl acetoacetate,
Aromatic tertiary amines, mercaptos and the like are included.
These polymerization accelerators can be used alone or in combination of two or more. The concentration of the polymerization accelerator in the polymerizable composition is, for example, 10 to 1000 ppm, preferably 10 to 1000 ppm.
It can be selected from a range of about 500 ppm (for example, 10 to 100 ppm), and may be about 30 to 50 ppm.

Curing (crosslinking) of the unsaturated polyester is possible at room temperature. However, in order to cure the polyester in a short time (for example, about 0.5 to 50 minutes), it is preferable to perform the curing at a temperature of about 60 to 200 ° C. It is advantageous.

[0053] The coating for coating the surface of the granular substrate may contain additives such as a binder. Examples of the binder include polyvinyl acetate, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, acrylic resin, vinyl chloride-vinyl acetate copolymer, and chlorine such as chlorinated polypropylene. Binder resins such as functionalized polyolefins and cellulosic resins such as acetylcellulose, and other binders. The binder can be used alone or in combination of two or more. The amount of the binder used can be selected according to the type of the cement setting retarding component and the like. When using a polymer capable of expressing a cement setting delay ability by hydrolysis, a binder is not necessarily required, for example, based on 100 parts by weight of the polymer,
The binder can be selected from a range of 0 to 200 parts by weight, preferably about 0 to 100 parts by weight. When a cement setting retarder is used, the setting retarder is, for example, 5 to 1000 parts by weight, preferably 10 to 7 parts by weight, based on 100 parts by weight of the binder.
00 parts by weight, more preferably about 25 to 500 parts by weight.

The additives other than the binder include fillers, stabilizers, plasticizers, defoamers, emulsifiers, hydrolysis accelerators, polymerization inhibitors, polymerization initiators, reactive diluents, and polymerization accelerators. No.

The shape and size of the cement setting retarding powder and granules are determined by the mode of use of the powder and the shape and size of the pattern (uneven pattern) formed on the surface of a concrete structure such as a surface decorative concrete product. Determined accordingly. The shape of the powder particles for cement setting retardation may be spherical (true sphere, elliptical), polyhedral, columnar, pyramidal, etc., or may have a complicated shape. The shapes may be the same or different. The size (average diameter) of the cement granulation delay powder is 0.1 μm to 50 cm (for example, about 1 μm to 50 cm, especially about 10 μm to 50 cm), preferably 50 μm to 20 cm, and more preferably about 100 μm to 15 cm. .

The specific gravity of the powder particles for delaying cement setting may be within a range that does not impair workability and operability. However, in order to prevent the powder from floating in bleed water, being washed away, or being blown by the wind. , For example, 1 or more (for example, about 1 to 10),
It is preferably about 1 to 5, more preferably 1.5 or more (for example, about 1.5 to 10, especially about 1.5 to 5),
It is often about 1.5 to 3.

In the powder for cement setting retardation of the present invention,
The surface of the powdery granular substrate does not necessarily need to be completely covered with the cement setting retarding component, and may be partially covered. In addition, each of the powder particles for delaying cement setting is composed of (A) a powdery granular substrate as a core (core) and a cement setting delay layer (coating) containing a cement setting delaying component that coats the substrate. And (B) a plurality (or a large number) of powdery or granular substrates may be dispersed in a matrix (coating) containing a cement setting retarding component.

The proportion occupied by the granular substrate in the cement setting retarding granular material can be appropriately selected according to the form of the granular material. For example, in the embodiment (A), the ratio of the granular substrate is 10% by weight or more and less than 100% by weight, preferably 30% by weight or more and less than 100% by weight, based on the whole granular material.
More preferably, it is about 50% by weight or more and less than 100% by weight. The ratio of the granular substrate in the form (B) is, for example, not less than 1% by weight and not more than 10% by weight based on the whole granular material.
Less than 0% by weight, preferably 10% by weight or more and 100% by weight
(E.g., 10 to 90% by weight), more preferably 1
It is about 5 to 70% by weight (for example, 20 to 50% by weight). The ratio of the granular substrate in the granular material for retarding cement setting is 10% by weight or more with respect to the whole granular material.
It is often less than 0% by weight.

In the above embodiment (A), the thickness of the cement setting retardation layer may be any thickness as long as the effect of retarding the setting of the cement can be exhibited.
μm (for example, 5 to 800 μm), preferably 10 to 50
It is about 0 μm (for example, 15 to 300 μm), and more preferably about 30 to 200 μm (for example, 60 to 150 μm).

The powder for cement setting retardation can be obtained, for example, as follows. For example, the (A)
Can be easily obtained by a conventional coating method. For example, a powdery or granular substrate having an appropriate shape and size can be obtained by coating with a coating solution containing the cement setting delay component and, if necessary, an additive such as a binder, and then drying or curing the coating solution. Can be.

The coating liquid may contain an organic solvent and / or water. As organic solvents, methanol,
Alcohols such as ethanol and isopropanol; aliphatic hydrocarbons such as hexane and octane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons; ketones such as acetone and methyl ethyl ketone , Ethers;
Esters such as ethyl acetate; aprotic polar solvents;
And a mixed solvent thereof.

The coating may be carried out by a conventional coating method, for example,
It can be performed by a method such as coating, dipping, spraying and the like.
Coating by spraying can be performed using, for example, a fluidized bed coating apparatus. Drying and curing (for example, curing of unsaturated polyester or the like) may be performed at room temperature, but since it is performed in a short time, for example, 60 to 200 ° C.
It is advantageous to do so.

The powder for cement setting retardation having the form (B) includes, for example, a powdery and granular base, a cement setting retarding component, and, if necessary, additives such as a binder. The mixture can be obtained by subjecting the mixture to a conventional granulation method, molding method, pulverization (crushing) method and the like. For example, the cement granulation delay granules may be prepared by mixing (1) a mixture containing a powdery or granular substrate, a powdery or granular cement setting retardant component, and if necessary, an additive such as a binder, with a tableting machine, a granulating machine, A mixture containing (2) (a) a powder-granular substrate and a polymer capable of exhibiting cement setting retarding ability by hydrolysis, or (b) a powder-granular substrate,
A mixture containing a cement setting retarder and a binder resin is melted and then solidified or hardened, or molded into an appropriate shape by a conventional molding method, for example, compression molding, extrusion molding, injection molding or the like. It can be obtained by adjusting to a desired size by cutting, pulverizing, crushing, classifying means or the like as required. As the additives such as the binder, those exemplified above can be used. As the granulator, a conventional granulator such as a fluidized bed granulator can be used, and for compression molding, extrusion molding and injection molding, a conventional molding machine for plastic molding can be used. The molding pressure and the molding temperature can be appropriately set depending on the type of the material to be molded. For example, in compression molding of a thermosetting resin, molding can be performed under temperature conditions equal to or higher than the curing temperature of the resin. As the pulverizing means, for example, those described above can be used.

The powder for delaying cement setting according to the present invention is useful for producing a concrete structure having a washed surface formed on a concrete surface. That is, in the state where the cement hardening delaying powder is in contact with the surface of the inorganic hardening composition, after curing the inorganic hardening composition, the cement hardening delay powder and non-hardening inorganic hardening By removing the composition, a concrete structure having a washout surface formed on the surface can be manufactured.

FIG. 1 is a schematic sectional view showing an example of the method for producing a concrete structure according to the present invention. In this example, a powder 2 for cement setting delay is laid on the bottom of a mold 1 so as to have a predetermined thickness to form a powder layer, and a plurality of decorative materials 3 are arranged thereon in a desired arrangement. And pressed into the granular material layer by pressing to a predetermined depth.

The size of the powder 2 for delaying cement setting is as follows:
An appropriate selection can be made within a range that does not impair the operation of inserting the decoration material. For example, the size (average particle size) of the powder 2 is
About 0.1 μm to 5 mm (for example, 10 μm to 5 mm),
Preferably about 20 μm to 3 mm, more preferably about 5 μm
It is about 0 μm to 1 mm. By using a powder having a small particle size (for example, a particle size of about 0.1 μm to 2 mm), a washout surface having a natural texture can be provided on a portion of the surface of the concrete structure other than the portion where the decorative material is fixed. Can be formed. In addition, by using a powder having a relatively large particle size (for example, a particle size of about 2 to 5 mm), the washing surface can be formed on the concrete surface, and an uneven shape corresponding to the shape of the powder 2 can be obtained. Can be formed.

The thickness of the granular material layer can be appropriately selected according to the depth of the joint groove between the decorative materials 3 in the desired concrete product, for example, 0.2 to 20 cm, preferably 0.5 to 10 cm. More preferably, it is about 1 to 8 cm.

As the decorative material 3, various materials, for example,
Cobble stone, black stone, natural stone such as iron flat stone, stone materials such as artificial stone,
Ceramic materials such as tile, glass, mortar or concrete, metal materials, wood, and woven fabrics can be used. The decorative material may be in any shape such as a lump, a flat plate,
The tile may be a normal tile, a mosaic tile, or a split tile. If the decorative material 3 has front and back,
It is placed so that the front (front) surface side is in contact with the granular material 2.

The pressing of the decorative material 3 may be performed individually,
Pressure may be applied to a plurality of decorative materials 3 at the same time. Decoration material 3
Is pressed into the granular material layer by pressing, the peripheral portion of the pressing portion usually protrudes in a convex shape. The indentation depth of the decorative material 3 can be set according to the depth of the joint groove to be formed. In addition, since the cement granulation delaying powder inhibits the hardening of the cement at the joint between the decorative materials 3, the depth of the joint groove is determined by the depth of indentation of the decorative material 3 and the setting delay depth at the joint (curing delay). (Depth affected by the delay action).

Next, an inorganic curable composition (curable composition containing cement) 4 is cast and cured by a conventional curing method such as curing. By removing the hardened inorganic curable composition, a surface-decorated concrete product (such as a precast concrete plate) to which the decorative material 3 is integrally fixed can be obtained.
In the production of a concrete product, a reinforcing material such as a reinforcing bar may be provided in the formwork and the inorganic curable composition may be cast as necessary.

In this method, since the granular material 2 is used, there is no need for a complicated operation of applying a cement setting retarder to a mold or attaching a woven cloth impregnated with the cement setting retarder. Further, unlike the case where paper or woven cloth is used, breakage or misalignment hardly occurs. Further, even if the decorative material 3 has a complicated shape, the joint groove having a predetermined depth can be formed by a simple operation of pressing.

Further, since the hardening at the contact surface with the inorganic curable composition 4 can be uniformly suppressed by the powder 2, it is possible to uniformly form the washing surface having a natural texture on the concrete surface. Furthermore, even if the decoration material has a complicated shape, such as a decoration material having an undercut, when the decoration material is pressed, the granular material flows and comes into contact with the decoration material in a state conforming to the outer shape of the decoration material. It is difficult for voids to be formed between the powder and the granules, so that the inorganic curable composition does not easily flow into the surface of the decorative material. Even if it flows, the hardening of the cement is suppressed by the cement hardening delay component on the surface of the granular material. Therefore, the operation of removing the "slow" can be extremely simplified.

Even if the uncured composition adheres to the surface or joint groove of the decorative material 3, it can be easily removed together with the powder 2 by a dry method such as a suction operation using a suction device. Further, the surface of the hardened concrete is washed with water, pressurized water, jet stream or the like to remove the non-hardened inorganic hardenable composition, so that the washed surface where the aggregate is exposed can be easily formed.

[0074] Polymers capable of exhibiting the ability to retard cement setting by hydrolysis as the cement setting retarding component, especially powders using the polyester, have the following advantages. That is, unlike other curing retarders, polyester hardly dissolves in water and hardly flows with bleed water from concrete. However, ester bond of polyester is hydrolyzed due to strong alkalinity of concrete, and carboxyl groups and hydroxyl groups useful for delay of curing are released. This hydrolysis rate increases as the moisture in the concrete is used to harden the cement, and is maximized by the heat generated by the concrete during curing, and the released carboxyl groups and hydroxyl groups synergistically exhibit a large hardening retarding ability. Let it. On the other hand, the concrete at the stage where the curing retarding ability is developed does not have fluidity already, and even if the curing retarding component is liberated due to hydrolysis of the polyester, it does not dissolve in bleed water and move. Therefore, the hardening delay ability can be exhibited only at a desired site, and a beautiful surface pattern can be accurately and clearly formed by washing out after hardening the cement.

FIG. 2 is a schematic sectional view showing another example of the method for producing a concrete structure according to the present invention. In this example, the inorganic curable composition 4 is poured into the mold 1, and the cement-curing delay powder 12 is sprayed thereon.
After curing, the mold 1 and the granular material 12 are removed, and the uncured inorganic curable composition remaining on the surface of the obtained cured concrete is removed by washing or the like.

The shape and size of the powder 12 are appropriately selected according to the pattern and decoration to be formed on the concrete surface. For example, an average particle size of 0.1 μm to 2 mm
(Eg, 10 μm to 2 mm), preferably 20 μm
By using the granular material 12 having a size of about 1 mm (for example, 50 μm to 1 mm), a clean washing surface can be formed on the concrete surface. In addition, when the granular material 12 having a relatively large particle size (for example, about 2 to 500 mm, and preferably about 2 to 200 mm) is used, in addition to the above-described washing surface, the shape of the granular material 12 An uneven shape can be formed. The powder particles 12 for delaying cement setting may be spread over the entire surface of the inorganic curable composition 4 or may be partially spread, for example, in a pattern. In addition, when the powder for cement setting retardation is sprayed on the upper surface of the inorganic curable composition as in this example, the powder having a specific gravity larger than 1 is particularly used so as not to be poured into the bleed water. It is preferred to use a body.

In this example, since the hardening on the contact surface with the inorganic curable composition 4 can be uniformly suppressed by the powder 12,
A beautiful wash surface having a natural texture is formed on the surface of the concrete product. In addition, since an uneven pattern corresponding to the shape of the granular material 12 is formed on the surface of the concrete product, by changing the shape and size of the granular material 12, concrete having various uneven shapes on the surface is formed. Products can be easily manufactured. In addition, the powder 12 can be easily removed together with the non-cured inorganic curable composition by a dry method using no water, such as suction, so that the surface finishing operation can be simplified. The individual shapes, sizes, and constituent materials of the powders 12 may be the same or different.

FIG. 3 is a schematic sectional view showing still another example of the method for manufacturing a concrete structure according to the present invention. This example is characterized in that a plurality of kinds of powder particles for delaying cement setting having different shapes and sizes are used. That is, form 1
The inorganic curable composition 4 is cast therein, and the particles 22a and 22b for delaying cement curing different in size are respectively spread (placed) thereon, and the inorganic curable composition 4 is cured. After that, the uncured inorganic curable composition remaining on the surface of the mold 1, the granules 22a and 22b, and the obtained cured concrete is removed by washing or the like. The powder 22 a is composed of the gravel 5 and the cement setting retardation layer 6 covering the surface of the gravel 5, and the powder 22 b is made of sand (not shown) having a smaller particle size than the gravel 5. And a cement setting delay layer (not shown) covering the surface of the sand.

In this example, since the hardening of the cement is suppressed at each contact portion between the inorganic curable composition 4 and the granules 22a and 22b, the uncured inorganic curable composition on the surface of the hardened concrete is removed. By doing so, it is possible to form a washed surface in which the aggregate is exposed on the surface, and, depending on the size of the granular material, the surface decorative concrete in which the surface has an uneven pattern corresponding to the shape of the granular material 22a or 22b. The product is obtained. The powders 22a and 22a
b is not limited to the above, and various powders and granules described in the description of the powder for granulation of the present invention can be used.

FIG. 4 is a schematic sectional view showing still another example of the method for producing a concrete structure according to the present invention. In this example, a mold is installed on the ground 7 as necessary, and the inorganic curable composition 4 is cast over a predetermined distance with a predetermined width, and then the cement setting delay powder particles 32 are sprayed. . Then, after the inorganic curable composition 4 is cured, the powder 32 and the uncured inorganic curable composition are removed to obtain a concrete pavement road.

The size (average particle size) of the powder particles 32 for retarding cement setting may be such that irregularities are formed on the concrete surface, for example, 10 μm to 1 cm, preferably 50 μm to 5 μm.
mm, more preferably about 100 μm to 1 mm, but a powder having a particle size exceeding 1 cm may be used. When the particle size of the powder body 32 is relatively small, as described above,
When the washing surface where the aggregate is exposed is formed on the concrete surface, and the particle size of the granular material 32 is relatively large, a concavo-convex shape corresponding to the shape of the granular material 32 is formed together with the washing surface.

The distribution density of the granules 32 varies depending on the size of the granules 32, but is, for example, 50 to 2000 g / m ² , preferably 100 to 10 g / m ^{2 on} the concrete surface.
00 g / m ² , more preferably 300 to 600 g / m ^{2
About 2} . The cement setting delay powder 32 may be spread over the entire surface of the inorganic curable composition 4, but may be spread partially, for example, in a desired pattern.

The powder 32 and the uncured inorganic curable composition can be easily removed by, for example, sucking with a suction device while brushing the concrete surface. The powder 32 and the uncured inorganic curable composition can also be removed by washing with water, pressurized water, or the like.

In this road, the hardening of the concrete is suppressed at the contact portion between the inorganic curable composition 4 and the granular material 32.
When the uncured inorganic curable composition is removed, an uneven surface (rough surface) where the aggregate is exposed is formed on the concrete surface. Therefore, the coefficient of friction with the tire on the road surface increases, and slip can be prevented. According to this method, it is possible to form an uneven surface for preventing slippage on a concrete pavement road by a simple operation of dispersing powder particles and removing it by suction, so it is compared with the conventional method of embedding a ring-shaped stone plate etc. on the road surface As a result, work efficiency can be greatly improved.

The cement contained in the inorganic curable composition includes, for example, air-hardened cement (lime such as gypsum, slaked lime and dolomite plaster); hydraulic cement (eg, Portland cement, early-strength Portland cement, alumina cement) , Slag cement, self-hardening cement such as high-hardened cement, baked gypsum, etc.
Blast furnace cement; mixed cement). Preferred cements include, for example, gypsum, dolomite plaster and hydraulic cement.

The cement may be used as a paste composition with water (cement paste), and may be used as a mortar composition or a concrete composition containing fine aggregate such as sand, silica sand, perlite, or coarse aggregate. May be. The paste composition and the mortar composition, if necessary,
Coloring agents, curing agents, curing accelerators such as calcium chloride, water reducing agents such as sodium naphthalene sulfonate, coagulants,
It may contain various additives such as a thickener such as carboxymethylcellulose, methylcellulose and polyvinyl alcohol, a foaming agent, a waterproofing agent such as a synthetic resin emulsion, and a plasticizer.

[0087]

According to the present invention, a washing surface can be simply and efficiently formed on the surface of a concrete structure. In addition, even when the mortar composition is cast, it is possible to suppress the occurrence of breakage or misalignment, etc., and it is possible to uniformly suppress the hardening at the contact surface with the mortar composition, and to prevent the mortar composition from being fixed at a predetermined position on the surface of the concrete structure. The washing surface can be formed with high accuracy. Further, it is useful for obtaining a concrete structure whose surface is decorated with a decorative material or the like, and even a decorative material having a complicated shape can be easily fixed to the surface of the concrete structure, and the decorativeness can be enhanced.

Further, according to the method for manufacturing a concrete structure of the present invention, a concrete structure having a washout surface formed on the surface can be simply and efficiently manufactured. In addition, the surface can be easily decorated with a decoration material while suppressing damage. Further, it is possible to manufacture a concrete structure in which a predetermined pattern is accurately formed at a predetermined portion. In addition, a concrete structure having a non-slip effect on its surface can be easily manufactured.

[0089]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 An autoclave having a capacity of 10 liters equipped with a stirring blade was placed in an autoclave.
3452 g (35.2 mol) of maleic anhydride and 2539 g (40.9 mol) of ethylene glycol were added, and hydroquinone as a polymerization inhibitor and tetra-n-butoxytitanium as a polymerization catalyst were each contained in a content of 100 p.
pm and 50 ppm. In order to stir the contents and remove water generated by the reaction, the temperature was raised from normal temperature to 150 ° C. over 3 hours under normal pressure while nitrogen gas was introduced, and further from 150 ° C. to 210 ° C. over 24 hours. The temperature was raised to stop the reaction. Diethylene glycol monomethacrylate 4 was added to 100 parts by weight of the obtained oily unsaturated polyester (weight average molecular weight 2250).
0 parts by weight, 3 parts by weight of an organic peroxide (manufactured by NOF CORPORATION; Perbutyl O), and 0.1 part of cobalt acetate as a crosslinking catalyst.
005 parts by weight were added and mixed to prepare a polymerizable composition.

Particle size 200-600 μm (average particle size 400
μm) of sand was placed in a Henschel mixer heated to 150 ° C., and 8 parts by weight of the polymerizable composition was sprayed over 3 minutes while stirring and mixing the contents. And
By further stirring and mixing for 7 minutes, a cement setting delay powder having a setting delay layer formed on the surface of sand was obtained.

[0092] The above-mentioned powder and granules are placed in a mold (60 cm x 55 c
m, a depth of 10 cm) and a 5 cm-thick granular material layer was provided. On this granular material layer, as a decorative material, 25 flat stones (about 10 cm in diameter x about 3 cm in thickness) are arranged in five rows and five rows, and pressure is applied from the back thereof.
Each stone was pushed into the sand layer to a depth of about 2 cm. Next, concrete was poured from above, and 50 ° C
After curing for 24 hours under the conditions described above, and left at room temperature for 24 hours, the mold was released. After demolding, the sand was blown off with a broom, and while spraying pressurized water, the broom was used to remove the surface of the decorative material and the "slow" joint grooves between the decorative materials. The "noto" was easily washed away, and a surface-decorated concrete plate having an extremely beautiful appearance was obtained without leaving any on the surface of the decorative material or the joint groove. In addition, the washing | cleaning surface which has a natural texture was formed in the joint groove part. The time required to remove the "slow" was about 2 minutes.

Example 2 Concrete was poured into a formwork (60 cm × 55 cm, depth 10 cm) at a height of 5 cm, rebars were arranged at intervals of 20 cm, and the concrete was further adjusted to a total height of 10 cm. It was cast. On the surface of the concrete, the granules for retarding cement setting prepared in the same manner as in Example 1 were sprayed (spray density: 600 g / cm ² ). Curing treatment was performed at 50 ° C. for 24 hours, left at room temperature for 24 hours, and then released. After removal from the mold, the powder was suctioned and removed with a vacuum cleaner while brushing, and the concrete surface was washed with a broom while applying pressurized water. The natural color of sand (aggregate) and the exposure of sand particles were exposed on the surface. A concrete plate on which a clean washing surface was formed was obtained.

Example 3 A flat stone (about 10 cm in diameter × about 3 cm in thickness) was immersed in a polymerizable composition prepared in the same manner as in Example 1 and then placed in an electric oven at 150 ° C. for 30 minutes. By heat treatment, a cement granulation retarding powder A having a stone with a curing retardation layer having a thickness of about 100 μm formed on the surface of the stone was obtained.

On the other hand, to 100 parts by weight of the polymerizable composition obtained in the same manner as in Example 1, 30 parts by weight of powdery zinc oxide having a particle size of about 150 μm or less (average particle size of about 20 μm) was added and mixed. Then, pour it into a stainless steel bat so as to have a height of 1 cm, put it in a 150 ° C. electric oven,
It was cured by heating for 0 minutes. The cured product was cooled to room temperature, pulverized with a pulverizer, and classified to obtain an average particle size of 200 μm in which the zinc oxide powder was dispersed in the unsaturated polyester.
m of cement setting delay powder B was obtained.

Form (60 cm × 55 cm, depth 10 c)
m), in the same manner as in Example 2,
0 cm, and then 25 pieces of the above-mentioned cement setting delaying powder and granules A were placed on the surface of concrete in a length and width of 5 cm each.
They were arranged in rows, and about half of the thickness was pushed into the concrete by pressing. And out of the concrete surface
The granules B were sprayed between the granules A. 50 ℃
After curing for 24 hours under the conditions described above, and left at room temperature for 24 hours, the mold was released. After removal from the mold, the powder A was removed, and the powder B was removed by suction using a vacuum cleaner. The concrete surface was washed with a broom while applying pressurized water. Was formed, and an uneven shape corresponding to the shape of the granular material A was formed at the position where the granular material A was disposed.

Example 4 A monomer formulation was prepared by adding 3136 g of maleic anhydride (32.0 g).
Mol), 531 g (3.2 mol) of terephthalic acid and 2538 g (40.9 mol) of ethylene glycol, and 100 parts by weight of the unsaturated polyester (weight average molecular weight 2200) obtained in the same manner as in Example 1. 20 parts by weight of diethylene glycol monoacrylate, 3 parts by weight of an organic peroxide (manufactured by NOF CORPORATION; Perbutyl O), and 0.005 parts by weight of cobalt acetate as a crosslinking catalyst were added and mixed to prepare a polymerizable composition. By the same operation as in Example 1 except that the polymerizable composition thus prepared was used,
A powder for delaying cement setting was obtained. After casting concrete with a width of 2 m on the ground, the powder for delaying cement setting was sprayed on the surface at a rate of about 500 g per m ² . After standing at room temperature for 3 days, the powder and unhardened concrete are removed by suction while brushing while brushing, and washed with water. As a result, an uneven surface with exposed aggregate is formed on the surface of the concrete pavement road. Was done.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing one example of a production method of the present invention.

FIG. 2 is a schematic sectional view showing another example of the production method of the present invention.

FIG. 3 is a schematic sectional view showing still another example of the production method of the present invention.

FIG. 4 is a schematic sectional view showing another example of the production method of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Mold frame 2, 12, 22a, 22b, 32 ... Powder for granulation of cement setting delay 3 ... Decorative material 4 ... Inorganic curable composition 5 ... Granular substrate 6 ... Curing delay layer 7 ... Ground

Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location // C08G 63/52 NPD C08G 63/52 NPD C04B 103: 24

Claims (18)

[Claims] 1. A cement / curing retardation powder / granule comprising a powdery / granular substrate and a coating covering the surface of the powdery / granular substrate, wherein the coating contains a cement setting retarding component. 2. The powder for granules for retarding cement setting according to claim 1, wherein the cement setting retarding component is a polymer capable of exhibiting cement setting retarding ability by hydrolysis. 3. The powder for delaying cement setting according to claim 2, wherein the polymer is an unsaturated polyester. 4. An unsaturated polyester comprising: a polyvalent carboxylic acid component containing an unsaturated polycarboxylic acid having a main chain having 4 to 6 carbon atoms or a derivative thereof; and a polyvalent having a main chain having 2 to 4 carbon atoms. 4. The powder for delaying cement setting according to claim 3, which is an unsaturated polyester obtained by reaction with a polyol component containing an alcohol or a condensate thereof. 5. The method of claim 1, wherein the unsaturated polycarboxylic acid is maleic acid,
The powder for delaying cement setting according to claim 4, which is maleic anhydride, fumaric acid or a derivative thereof. 6. The cement / curing retardation powder according to claim 4, wherein the polycarboxylic acid component further contains an aromatic polycarboxylic acid. 7. The powder for delaying cement setting according to claim 4, wherein the polyhydric alcohol is ethylene glycol, propylene glycol, glycerin or a condensate thereof. 8. The powder for delaying cement setting according to claim 3, wherein the unsaturated polyester has a weight average molecular weight of 300 to 100,000. 9. The cement / curing delay powder according to claim 3, wherein the unsaturated polyester is a cured product obtained by crosslinking. 10. The cement / curing delay powder according to claim 9, wherein the cured product is a cured product of a polymerizable composition containing an unsaturated polyester, a polymerizable vinyl monomer and a polymerization initiator. 11. The powder for granulating cement setting retardation according to claim 1, wherein the cement setting retarding component is a cement setting retarder. 12. The cement setting retarder comprises phosphoric acid or a salt thereof, boric acid or a salt thereof, hexafluorosilicate, phosphonic acids, oxycarboxylic acids, keto acids, polyhydric phenols, lignin sulfonic acids and saccharides. 12. The cement / curing delay powder according to claim 11, which is at least one selected from the group consisting of: 13. The cement-delayed powdery granule according to claim 1, wherein the powdery or granular substrate is at least one selected from a powdery metal, a powdery ceramic, an inorganic molded product, and a resin molded product. 14. A method for producing a concrete structure having a scoured surface formed on a surface thereof, wherein the powder for cement setting retardation according to claim 1 is brought into contact with the surface of the inorganic curable composition, thereby setting the inorganic material. A method for producing a concrete structure, comprising removing a cement setting delay powder and a non-cured inorganic curable composition after curing a curable composition. 15. The method for producing a concrete structure according to claim 14, wherein the powder particles for delaying cement setting are removed by suction. 16. A layer of cement-curing delay powder or granules is provided at the bottom of a mold, a decorative material is provided thereon, and an inorganic curable composition is cast and cured to form a mold. Remove the cement hardening delay granules and uncured inorganic curable composition,
The method for producing a concrete structure according to claim 14, wherein a surface-decorated concrete product having a decorative material fixed to the surface is obtained. 17. Placing an inorganic curable composition in a mold,
15. A cement granulation retarding powder is sprayed on the surface thereof, and the inorganic curable composition is cured, and then the mold, the cement curing retarding powder and the non-cured inorganic curable composition are removed. A method for producing the concrete structure according to the above. 18. An inorganic curable composition is cast on a ground with a predetermined width over a predetermined distance, and particles for cement setting delay are sprayed on the surface thereof, and after the inorganic curable composition is cured. The concrete pavement road is obtained by removing the cement-curing delay powder and the uncured inorganic curable composition.
5. The method for producing a concrete structure according to 4.