JPH1036154A - Resin suspension for retarding hardening of cement and production of concrete structure utilizing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin suspension for retarding the hardening of a cement useful for forming an aggregate exposed finish surface by washing or a pattern on the surface of a concrete product with a good accuracy. SOLUTION: This resin suspension for retarding the hardening of a cement comprises polymer particles capable of manifesting the ability to retard the hardening of the cement by hydrolysis. The polymer constituting the polymer particles includes an unsaturated polyester prepared by reacting a polyvalent carboxylic acid component such as maleic acid with a polyol component such as ethylene glycol. The unsaturated polyester may be a cured product. The resin suspension for retarding the hardening of the cement or a resin composition obtained by removing the solvent from the resin suspension is brought into contact with the surface of an inorganic hardenable composition to carry out the hardening treatment of the inorganic hardenable composition. The unhardened inorganic hardenable composition can then be removed from the surface of the resultant concrete hardened product to thereby produce a concrete structure in which the aggregate exposed finish surface by washing is formed on the surface.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin suspension for delaying the setting of cement, which is useful for delaying the setting of a curable composition containing cement, and to a method for producing a concrete structure using the same.

[0002]

2. Description of the Related Art A cement setting retarder is a type of cement admixture mixed with cement to delay the setting and setting of mortar or concrete by delaying the hydration reaction of cement. Regarding cement setting retarders, JP-A-1-172250 discloses inorganic setting retarders such as lead oxide, boron oxide, borax, zinc chloride, zinc oxide and magnesium silicofluoride, and polyhydroxy compounds (sugar, alcohol, methylcellulose). , Ethyl cellulose, polyvinyl alcohol, dextrin, etc.), sodium polyacrylate, oxycarboxylate, lignin sulfonate, gluconic acid or a salt thereof, pyruvic acid,
Organic curing retarders such as keto acids such as α-keto glutaric acid are described. The purpose of using these cement setting retarders is to transport ready-mixed concrete over a long period of time while suppressing hardening in the summer, and to alleviate the stress caused by temperature in large concrete structures.

[0003] In addition, it is often practiced to decorate the surfaces of concrete moldings and various buildings by 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 washing with water immediately before the cement hardens to wash out the mortar of the concrete surface layer. In this method, since the curing speed of concrete is closely related, the timing of washing out is limited to a very narrow range in terms of time, mass production,
Or it is an unsuitable technology for application to large buildings.

[0004] Regarding the application of tiles to the surface of concrete, there has been proposed a method of using unit tiles in which a plurality of tiles are attached and arranged on the surface of an adhesive layer of an adhesive tape. 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 order to solve such a problem, it is necessary to apply the cement setting retarder to inhibit the hardening of only the concrete surface layer, to process the surface of the concrete product, or to form a pattern on the surface. Proposed. For example, a paper is impregnated with a curing retarder, the impregnated paper is fixed to the bottom of a mold by sticking or the like, mortar is poured, and after the concrete is hardened, the concrete molded product is released from the mold and contacted with the impregnated paper. By washing off the uncured mortar on the surface,
A method of exposing aggregate and obtaining a natural texture has been proposed. JP-A-63-216703 discloses a process of cutting a pattern paper impregnated with a curing retarder into a paper to produce a cutting pattern paper corresponding to a predetermined character or graphic pattern.
A step of bonding a cutting pattern to a predetermined portion of the inner surface of the form, a step of casting a mortar composition into the form and curing, a step of disassembling the form and taking out a concrete product, a pattern portion of the concrete product, After the washing step, a predetermined uneven pattern is formed on the surface of the concrete product. JP-A-61-202803 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.

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.

However, conventional setting retarders that suppress the hydration mechanism of cement have high solubility in water, and dissolve 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. For this reason, the curing retarder flows into a portion where washing is not required, or the curing retarder is locally concentrated, but the curing retarder flows out in a portion where washing or decoration is required. In addition, on the surface through which the bleeding water has passed, the washing depth is particularly deep. Therefore, it is difficult to form a uniform washout surface at a predetermined portion of the surface of a concrete molded product or a building, or to form a pattern such as a decorative character or a figure with high accuracy.

[0008]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a cement setting retarding resin suspension which is useful for accurately forming a washout surface and a pattern on the surface of a concrete product.

Another object of the present invention is to provide a resin suspension for cement setting retardation which can easily and efficiently form a washout surface and a pattern on the surface of a concrete product.

It is still another object of the present invention to provide a cement setting retarding resin suspension useful for obtaining a surface-decorated concrete product whose surface is decorated with a decorative material while suppressing damage.

Another object of the present invention is to provide a method for easily and efficiently producing a concrete structure having a surface on which a washout surface and a pattern are accurately formed.

Still another object of the present invention is to provide a method for easily producing a surface decorative concrete structure having a high decorative property without damaging the decorative material.

[0013]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object. As a result, when a resin dispersion containing polymer particles capable of exhibiting the ability to retard cement hardening by hydrolysis is used, inorganic hardening can be achieved. It has been found that the hardening of the cement is uniformly suppressed in the contact portion of the conductive composition with the polymer particles, and a uniform washout surface and pattern can be easily formed on the surface of the concrete structure, and the present invention has been completed.

That is, the present invention provides a cement setting delay resin suspension containing polymer particles capable of expressing cement setting delay ability by hydrolysis.

The polymer constituting the polymer particles includes unsaturated polyester and the like. An unsaturated polyester is 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 polyhydric alcohol having a main chain having 2 to 4 carbon atoms or a condensate thereof. And an unsaturated polyester obtained by a reaction with a polyol component containing Further, the unsaturated polyester may be a cured product by crosslinking.

The present invention also relates to a method for producing a concrete structure having a scoured surface formed on the surface thereof, wherein the resin suspension for cement setting retardation or the suspension thereof is coated on the surface of an inorganic curable composition. Concrete structure for removing a solvent from a liquid, contacting a resin composition obtained, curing the inorganic curable composition, and then removing an uncured inorganic curable composition from the surface of the obtained cured concrete product. And a method for producing the same.

The present invention further relates to a method for producing a surface-decorated concrete structure integrated with a decorative material, wherein the resin suspension for delaying cement setting according to claim 1 is applied or impregnated on the surface of a substrate. Forming a cement setting delay layer composed of polymer particles capable of expressing a cement setting delay ability by hydrolysis, disposing a decorative material on the cement setting delay layer, and casting an inorganic setting composition. The present invention provides a method for producing a concrete structure, comprising removing the uncured inorganic curable composition after the mold is cured.

In the present specification, unless otherwise specified, the term "cement" means an inorganic substance which 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 term “sheet” refers to a two-dimensional structure regardless of thickness, and is used to include a film. Further, the “adhesive or adhesive” may be collectively referred to as “adhesive”. 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.

[0019]

DETAILED DESCRIPTION OF THE INVENTION The resin suspension for cement setting retardation of the present invention contains polymer particles. The polymer constituting the polymer particles is not particularly limited as long as it is a polymer capable of exhibiting the ability to retard cement setting by hydrolysis. Examples of such a polymer include a group capable of producing a group having a cement setting delaying ability such as a hydroxyl group or a carboxyl group by hydrolysis, for example, a polymer having an ester group. Examples of the polymer include polyester and the like. 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. Polycarboxylic acids include saturated polycarboxylic acids having 2 to 6 carbon atoms in the main chain such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid; maleic acid, maleic anhydride, fumaric acid, itacone 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, 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 2500). When polyethylene glycol is used, the weight average molecular weight is 300 or less. Often.

If necessary, the polyhydric alcohol may be used in combination with another polyol, for example, trimethylolethane, trimethylolpropane, pentaerythritol and the like. Of these polyesters, unsaturated polyesters,
Particularly, an unsaturated polyester containing maleic acid or maleic anhydride as a polycarboxylic acid component is 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.

The 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 cured product by crosslinking. 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 functional groups (hydroxyl group, carboxyl group, glycidyl group, etc.) such as acrylic acid and glycidyl (meth) acrylate, (meth) acrylic acid and the above-mentioned polyhydric alcohols (in particular, glycols such as polyethylene glycol and polypropylene glycol) With esters (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, and olefin monomers such as ethylene and propylene. 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 glycol (meth) acrylates. 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. Part (for example,
1 to 100 parts by weight), preferably about 5 to 200 parts by weight (for example, 5 to 100 parts by weight).
It may be in the range of about 30 parts by weight.

The cured product of the unsaturated polyester is composed of the components constituting the polymerizable composition (that is, the unsaturated polyester constituting the polymerizable composition (i), a polymerization initiator,
A cured product of the polymerizable composition (iii) containing a polymerization accelerator in addition to the unsaturated polyester and the polymerizable vinyl monomer and the polymerization initiator constituting the polymerizable composition (ii) may be used. Examples of the polymerization accelerator include organic acid cobalt salts such as cobalt naphthenate and cobalt octylate, acetylacetone, β-diketones such as ethyl acetoacetate, and β-diketones.
Ketoesters, 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 500 ppm (for example, 10 to 100 ppm).
pm), and may be about 30 to 50 ppm. Curing (crosslinking) of unsaturated polyester
Is possible at room temperature, but for a short time (for example, 0.5 to
(About 50 minutes) to cure at a temperature of 60 to 200
It is advantageous to carry out at about ° C.

As a dispersion medium (solvent) of the cement setting retardation suspension, water or an organic solvent can be used, and a mixture of two or more solvents may be used. The organic solvent can be selected according to the type of the polymer particles that are dispersoids. Examples thereof include alcohols such as methanol, ethanol, and isopropanol; aliphatic hydrocarbons such as hexane and octane; and alicyclic hydrocarbons such as cyclohexane. ;benzene,
Aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons; ketones such as acetone and methyl ethyl ketone; ethers; esters such as ethyl acetate; and aprotic polar solvents. Preferred dispersion media include water and alcohols such as methanol (for example, C
_1-3 alcohols) and mixed solvents thereof. Water is often used as the dispersion medium.

The content of the polymer particles in the resin suspension for cement setting retardation of the present invention can be appropriately selected within a range that does not impair the dispersion stability, and is, for example, 5 to 80% by weight, preferably 10 to 60% by weight. %, More preferably 20 to 50
% By weight.

The particle size of the polymer particles may be within a range that does not impair the dispersion stability, mechanical stability, film forming property, etc., and is, for example, 0.01 to 500 μm, preferably 0.01 to 200 μm, and more preferably 0.01 to 200 μm. Preferably 0.01 to 1
It is about 00 μm.

The viscosity of the resin suspension for cement setting retardation is
It can be appropriately set within a range that does not impair the handling property, dispersion stability, and the like, and is, for example, about 2000 to 100,000 centipoise, preferably about 5,000 to 20,000 centipoise, and more preferably about 7,000 to 15,000 centipoise.

The resin suspension for cement setting retardation may contain a cement setting retarder in addition to the polymer capable of exhibiting cement setting delaying ability by the hydrolysis. The cement setting retarder may be any setting retarder or setting retarder that reduces 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, polyhydric carboxylic acids, keto acids, polyhydric phenols, saccharides, humic acids, ligninsulfonic acids, monomers having a carboxyl group, or copolymers or salts thereof are included.

As the phosphonic acids, 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, oxycarboxylic acids, keto acids, polyhydric phenols, saccharides, lignin sulfonic acids and the like are preferable. These cement setting retarders can be used alone or in combination of two or more. The content of the cement setting retarder is, for example, 0 to 10 parts by weight based on 100 parts by weight of the polymer particles.
00 parts by weight (for example, 5 to 1000 parts by weight), preferably 0 to 700 parts by weight (for example, 10 to 700 parts by weight),
More preferably, it is 0 to 500 parts by weight (for example, 25 to 5 parts by weight).
00 parts by weight).

The resin suspension for cement setting retardation of the present invention usually contains a dispersant in order to enhance the dispersibility of the polymer particles.

Examples of the dispersant include anionic surfactants (eg, sodium dodecylbenzenesulfonate, sodium alkyldiphenyletherdisulfonate, sodium alkylnaphthalenesulfonate, sodium lauryl sulfate, sodium polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl Sodium phenyl ether sulfate, sodium dialkyl sulfosuccinate, etc.), cationic surfactants (eg, alkyltrimethylammonium salt), nonionic surfactants (eg, polyoxyethylene lauryl ether, polyoxyethylene oleyl phenyl ether, polyoxyethylene nonyl) Surfactants such as phenyl ether and oxyethylene / oxypropylene block copolymer);
Protective colloids such as proteins, vegetable rubber, and water-soluble polymers can be used. The amount of the dispersant used is, for example, 0.01 to 10% by weight based on the polymer particles,
Preferably 0.02 to 5% by weight, more preferably 0.1 to 5% by weight.
It is about 0.5 to 2% by weight.

The resin suspension for cement setting retardation also comprises:
It may contain an adhesive or an adhesive. Examples of the pressure-sensitive adhesive or adhesive include rubber-based pressure-sensitive adhesives such as natural rubber and synthetic rubber (eg, neoprene and isoprene), vinyl acetate-based elastomers such as polyvinyl acetate and ethylene-vinyl acetate copolymer, and acrylic rubber. An emulsion of an adhesive such as an acrylic elastomer or a polyester elastomer may be used, or a solvent-based adhesive may be used. Also, water-soluble viscous substances, for example, polyvinyl alcohol, polyacrylic acid or a salt thereof, polyacrylamide, methylcellulose, hydroxyethylcellulose, synthetic water-soluble polymers such as carboxymethylcellulose, locust bean gum, guar gum, gum arabic, tragacanth gum, pectin, Sodium alginate,
Natural water-soluble polymers such as carrageenin can also be used.
These pressure-sensitive adhesives or adhesives can be used alone or in combination of two or more. The pressure-sensitive adhesive may be used in combination with a tackifier (for example, a hydrocarbon resin such as a petroleum resin, a terpene resin, or a dicyclopentadiene resin, or a rosin derivative).

In the case of a cement-setting retarding resin suspension containing an adhesive or an adhesive, the suspension is applied or impregnated on a base sheet, a bottom plate of a mold, or the like to form a cement setting delay constituted by the polymer particles. When the layer is formed, the adhesiveness to a base sheet or the like can be improved. In addition, a decorative material or the like used for surface decoration of a concrete structure can be adhered to the cement setting retardation layer, so that the decorative material can be prevented from being shifted, detached, or dropped. In addition, in the cleaning and makeup work of the obtained surface decorative concrete structure, in order to efficiently clean the concrete surface and the surface of the decorative material, the adhesive or the adhesive is of such an extent that the decorative material can be temporarily fixed. In the case where a material capable of imparting adhesive strength or adhesive strength or a decorative material is firmly bonded, a material which can be removed by washing is preferable.

The content of the pressure-sensitive adhesive or adhesive may be within a range in which the curing retardation property is not impaired.
0 to 2000 parts by weight (for example, 1 to 100 parts by weight)
2000 parts by weight), preferably about 0 to 500 parts by weight (for example, 2 to 500 parts by weight), and more preferably about 0 to 50 parts by weight (for example, 3 to 50 parts by weight).

[0045] The resin suspension for cement setting retardation also includes
A thickener may be added in order to improve handleability, film forming property, and the like. Examples of the thickener include oxides such as silica, alumina, zinc oxide, iron oxide, titanium oxide, and magnesium oxide (eg, oxides of Group 1 to 15 elements); diatomaceous earth, kaolin, talc, bentonite,
Clays and minerals such as clay, stone powder, volcanic ash, coal ash; carbon black, graphite; metal powders such as iron powder and aluminum powder; alkaline earth metal salts such as calcium carbonate and barium sulfate; calcium hydroxide and magnesium hydroxide And alkaline earth metal hydroxides such as molybdenum disulfide.

The content of the thickener may be within a range that does not impair the curing retardation property, and is 0 to 2000 parts by weight (for example, 1 to 2000 parts by weight), preferably 0 to 2000 parts by weight based on 100 parts by weight of the polymer particles. To 500 parts by weight (for example, 2 to 50 parts by weight)
0 parts by weight), more preferably about 0 to 50 parts by weight (for example, 3 to 50 parts by weight).

The resin suspension for cement setting retardation may further contain, if necessary, other additives such as a binder, a surface conditioner, a preservative, an antifoaming agent, a plasticizer, a stabilizer, an antioxidant, UV absorbers, colorants, extenders, fillers, antistatic agents,
It may contain a polymerization inhibitor and the like.

The resin suspension for retarding cement setting of the present invention can be easily prepared by a method usually used for obtaining a resin suspension. For example, a resin suspension for cement setting retardation is obtained by polymerizing a monomer of a polymer capable of exhibiting cement setting delaying ability by hydrolysis by a conventional polymerization method (eg, bulk polymerization, solution polymerization, suspension polymerization, etc.). The polymer can be prepared by pulverizing and classifying the obtained polymer to a desired size, if necessary, and dispersing it in an appropriate solvent. The pulverization may be performed by any of dry pulverization and wet pulverization. For the pulverization, a conventional pulverizing means, for example, a jaw crusher, a hammer mill, a cone mill, a roll crusher, a ball mill, a vibration ball mill, a jet mill, a cutter mill, or the like can be used. Dispersion can be performed by a conventional stirring means, shaking means and the like. By using a homogenizer, a super mixer, or the like as the stirring means, the dispersion efficiency and dispersibility can be significantly improved.

Since the resin suspension for cement setting retardation of the present invention contains polymer particles capable of exhibiting cement setting delaying ability by hydrolysis, the polymer particles are hydrolyzed when contacted with an inorganic curable composition containing water. It is decomposed and the setting of cement is delayed and suppressed. In addition, since the polymer particles are dispersed in the solvent, the handleability is superior to that of a powder or a viscous liquid, and the cement setting delay layer composed of the polymer particles is uniformly formed on a substrate such as a base sheet. And it can be easily formed. Therefore, by washing out after hardening of the cement, the surface of the concrete structure was formed to have a washed-out surface having a natural texture with exposed aggregates, or patterns such as characters and figures were formed, and further integrated with the decorative material It is extremely useful in producing concrete products.

A concrete structure having a washout surface can be manufactured, for example, by the following method. That is, on the surface of the base sheet, the cement setting delay resin suspension is applied or impregnated, and dried to form a cement setting delay layer composed of the polymer particles, thereby producing a cement setting delay sheet. I do. Then, the sheet is disposed in a mold by pasting or the like so that the curing retardation layer becomes the surface, and an inorganic curable composition (a curable composition including cement) is poured in, and the sheet is cured by a conventional method such as curing. After the curing treatment by the curing method, the mold and the sheet are removed, and the uncured inorganic curable composition is removed from the surface of the resulting cured concrete, whereby the concrete with a washed surface formed on the surface Structures can be manufactured.

As the base sheet, for example, a non-porous sheet such as a plastic sheet or a metal foil, a porous sheet such as paper, woven fabric or non-woven fabric, or the like can be used. The polymer constituting the base sheet is not particularly limited, and examples thereof include polyolefins such as polyethylene and polypropylene; polyesters such as polyethylene terephthalate and polybutylene terephthalate (especially polyalkylene terephthalate); ethylene-vinyl acetate copolymer and ethylene-acrylic acid Copolymer; acrylic resin; polystyrene; polyvinyl chloride; polyamide; polycarbonate; polyvinyl alcohol, ethylene-vinyl alcohol copolymer, and the like. One or more of these polymers can be used. Preferred substrate sheets include plastic sheets and nonwoven fabrics using polyalkylene terephthalate such as polyethylene terephthalate. The base sheet may be a single-layer sheet or a composite sheet in which a plurality of layers are laminated. Further, the base sheet may be an unstretched sheet or a uniaxial or biaxially stretched sheet. Further, the surface of the base sheet may be surface-treated by a flame treatment, a corona discharge treatment, a plasma treatment, or the like.

The thickness of the base sheet is not particularly limited, but is, for example, 5 to 500 μm (for example, 5 to 400 μm).
m), preferably 10 to 300 μm (for example, 10 to 2 μm).
00 μm), more preferably about 15 to 150 μm (for example, 20 to 100 μm). In addition, the thickness of the cement setting retardation layer may be any thickness as long as the effect of delaying the setting of cement is exhibited, for example, 1 to 2000 μm.
(For example, 5 to 1500 μm), preferably 10 to 12
It is about 00 μm, and more preferably about 50 to 1000 μm.

The application of the resin suspension for cement setting delay
Application means used for ordinary coating, for example, dip coater, roll coater, gravure coater,
An air knife coater, reverse roll coater, comma coater, bar coater, curtain coater, spray and the like can be used. Since the suspension can be easily and uniformly applied, a spray method or the like is widely used.

The cement setting retarding sheet obtained as described above can exert a setting delay effect evenly on the cast inorganic setting composition by the setting delay layer having a uniform thickness. Even if the curing retardation layer is thin, high curing retardation can be imparted. Further, there is an advantage that it can be reinforced by the base film and is excellent in handleability.

By cutting the sheet into a shape corresponding to a desired pattern or the like and using the sheet, a washout surface on which the pattern, aggregate, etc. are exposed is formed in a portion of the surface of the concrete structure that comes into contact with the sheet. it can.

The uncured inorganic curable composition on the surface of the cured concrete can be easily removed by washing with water, pressurized water, jet stream or the like. In cleaning, a brush, a brush, or the like may be used to remove the uncured mortar composition. Uncured mortar composition, unreacted polymer particles, and the like can also be removed by a dry method such as suction.

A concrete structure having a washed surface formed on the surface can also be obtained by the following method. That is, the concrete structure is formed by coating or impregnating the cement suspension of the resin for delaying cement setting on the bottom plate of a mold, drying the cement, and forming a cement setting delay layer composed of the polymer particles. The composition can be manufactured by casting a hardening composition and performing a hardening treatment, then removing the mold, and removing the non-hardened inorganic hardenable composition from the surface of the hardened concrete obtained by washing or the like. In this method, the application of the resin suspension for cement setting retardation can be performed by the same method as described above. The thickness of the cement setting delay layer is the same as that of the setting delay layer in the cement setting delay sheet.

In this method, since the suspension is applied directly to the bottom plate of the mold, there is no need to peel off the base sheet after curing, and the working efficiency can be improved.

In the case of a concrete structure having a washed surface formed on a concrete surface, an inorganic curable composition is poured into a mold and the above-mentioned resin suspension for cement setting delay is sprayed on the surface of the composition. After the solvent is removed by drying or the like, the inorganic curable composition is cured by a conventional means such as curing, demolding, and an uncured inorganic curable composition from the surface of the obtained concrete cured product. Can also be produced by removing.

The resin suspension for cement setting retardation may be sprayed on the entire surface of the inorganic curable composition, or may be sprayed partially, for example, in a pattern. The method of spraying is not particularly limited, but a method capable of uniformly spreading, such as a spray method, is preferred.

The spraying amount (spraying density) of the resin suspension for cement setting retardation may be such that a washout surface can be formed on the concrete surface. And 1
0 to 2000 g / m ² , preferably ^{20 to} 1000 g / m ²
m ² , more preferably about 30 to 300 g / m ² .

Further, a concrete pavement road having an irregular shape formed on the concrete surface can be obtained by using the resin suspension for cement setting retardation of the present invention. For example, an inorganic curable composition is poured over a predetermined width and a predetermined distance on the ground, and the resin suspension for cement setting delay is sprayed on the surface thereof, and after removing the solvent as necessary, the inorganic curable composition is removed. Concrete-paved roads are obtained by curing the curable composition and removing the uncured inorganic curable composition from the surface. In this concrete road, since a washout surface having an uneven shape is formed on the surface, the coefficient of friction with the tire increases, and slip can be prevented.

The resin suspension for cement setting retardation may be sprayed on the entire surface of the inorganic curable composition, or may be sprayed partially, for example, in a pattern. Spraying amount (spraying density) of resin suspension for cement setting delay, cleaning method after curing,
Same as above. According to this method, since irregularities can be formed on the road surface by simple means such as spraying, the work efficiency can be greatly improved as compared with the conventional method of embedding a ring-shaped stone plate or the like in the road surface.

The polymer constituting the polymer particles contained in the resin suspension for cement setting retardation of the present invention exhibits a cement setting retarding ability by hydrolysis. Therefore, when initially contacted with the inorganic curable composition, the cement hardening retarding ability is hardly exhibited, but it is hydrolyzed by the strong alkalinity of uncured mortar or concrete, and the components useful for retarding the curing gradually liberate, and the cement setting retardation is delayed. The ability will be demonstrated. The rate of this hydrolysis increases as the hardening of the cement in the inorganic hardening composition progresses, and is maximized by the heat generation of the concrete during curing, and further, in the case of heat curing, by the heating, and a large cement hardening delay ability. Is expressed. On the other hand, although the concrete at the stage where the curing retarding ability is expressed is still in an uncured state, it does not have fluidity already, and even if the curing retarding component is released by hydrolysis, it no longer dissolves and moves in bleed water. .
Therefore, the hardening delay ability can be exhibited only at a desired portion, and the surface of the concrete structure can be beautifully finished by washing out after hardening the cement, and a pattern such as a character or a picture can be formed with high accuracy.

The surface decorative concrete structure integrated with the decorative material can be manufactured, for example, by the following method. That is, the cement setting delay resin suspension is applied or impregnated on the surface of the substrate, dried, and formed into a cement setting delay layer composed of polymer particles capable of expressing cement setting delay ability by hydrolysis. A decorating material is provided on the cement setting delay layer, and if necessary, the decorating material is pushed into the setting delay layer, an inorganic curable composition is cast, and curing is performed by a conventional method such as curing. After removing the mold, remove the non-cured inorganic curable composition, and if necessary, wash the surface of the decorative material fixed to the obtained concrete cured product, so that the decorative material is integrally fixed to the surface Concrete structures (decorative finishing blocks, precast concrete, etc.) can be obtained.

As the substrate, the above-mentioned substrate sheet, a bottom plate of a concrete formwork and the like can be used. When the base sheet is used as a base, a sheet having a hardening delay layer formed on the surface of the base sheet may be provided in a mold, and a decorative material may be provided on the hardening delay layer. When the bottom plate of the concrete form is used as the base, the decorative material can be directly disposed on the hardening delay layer formed on the bottom plate. The application method and the cleaning method described above can be used for applying the suspension and cleaning the surface of the decorative material.

As the decorative material, various materials, for example, natural stones such as cobble stone, black stone, iron flat stone, stone materials such as artificial stones, ceramic materials such as tiles, metal materials, glass materials, wood, woven fabrics and the like are used. You. The decorative material may be flat,
The tile may be a normal tile, a mosaic tile, or a split tile. In addition, in order to form a joint groove between the decorative materials, a padding such as a joint rod may be applied as necessary. According to this method, even when the inorganic curable composition reaches the surface side of a decorative material such as a tile, the curing of the inorganic curable composition can be suppressed by the curing retarding component generated by hydrolysis, and the non-cured (semi-cured or uncured) Cured) state,
The surface finish for removing the inorganic curable composition from the surface of the decorative material can be efficiently and completely performed by a simple operation such as washing with water.

In addition to the above-mentioned applications, the resin suspension for cement setting retardation of the present invention may be used in the same manner as conventional setting retarders, for example, for suppressing the hardening of ready-mixed concrete for a long period of time in summer, It may be added to an inorganic curable composition such as mortar or concrete for the purpose of, for example, reducing stress due to temperature in a concrete structure.

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, rapid cement). Self-hardening cement such as hard high-strength cement and calcined gypsum; lime slag cement, blast furnace cement and the like; 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, or pearlite, 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.

[0071]

According to the resin suspension for cement setting retardation of the present invention, a pattern or a washing surface can be accurately formed on the surface of a concrete product. Further, a washout surface and a pattern can be simply and efficiently formed on the surface of the concrete product. Further, it is possible to obtain a surface-decorated concrete product whose surface is decorated with a decorative material or the like while suppressing damage.

According to the method for manufacturing a concrete structure of the present invention, a concrete structure having a washed-out surface and a pattern formed with high precision on its surface can be simply and efficiently manufactured. In addition, a highly decorative surface decorative concrete structure can be easily manufactured without damaging the decorative material.

[0073]

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 A 10-liter autoclave equipped with a stirring blade was placed
While adding 3452 g (35.2 mol) of maleic anhydride and 2539 g (40.9 mol) of ethylene glycol, 100 ppm of hydroquinone as a polymerization inhibitor was added.
Tetra-n-butoxytitanium 50 pp as polymerization catalyst
m was added. While stirring the contents and flowing nitrogen gas to remove water generated by the reaction, under normal pressure,
After raising the temperature from room temperature to 150 ° C. over 3 hours,
The temperature was raised from 200C to 210C over 24 hours to stop the reaction. The obtained unsaturated polyester is cooled to 80 ° C,
Oily unsaturated polyester (weight average molecular weight 2250) 1
100 parts by weight, 40 parts by weight of diethylene glycol monomethacrylate, organic peroxide (Nippon Oil & Fats Co., Ltd.)
Co., Ltd., 3 parts by weight) and cobalt acetate as a crosslinking catalyst at a concentration of 50 ppm were added and mixed to obtain a polymerizable composition. The polymerizable composition was poured into a stainless steel vat (25 cm × 40 cm × 5 cm) so as to have a height of 2 cm, and was cured by heating at 120 ° C. for 15 minutes in a furnace.

The cured product was cooled to room temperature, coarsely pulverized by a crusher, further pulverized by a freeze pulverizer, and classified to obtain a powdery resin having a particle size of 100 μm or less (average particle size of about 60 μm).

In 1200 ml of water, 500 g of the above powdery resin, 0.5 g of polyoxyethylene lauryl ether as a dispersant, and sodium polyacrylate 3 as an adhesive were used.
0 g and 150 g of polyvinyl acetate emulsion (solid content 30% by weight) were added, and the mixture was vigorously stirred with a stirrer.
A resin suspension for delaying cement setting was obtained. The viscosity of this suspension was about 10,000 centipoise. Then, width 5
cm tape (polyethylene terephthalate film)
On one side of the, the cement setting delay resin suspension,
It was applied so that the thickness of the dried resin layer would be 500 μm, and left at room temperature for 24 hours to dry. The obtained tape is put into a wooden concrete plate form (internal volume 1m × 1m ×
(Depth: 10 cm) The resin layer was stuck on the bottom surface at an interval of 10 cm with the resin layer facing upward. A mortar of Portland cement / sand / water = 100/200/55 (weight ratio) is cast into a mold so as to have a height of 3 cm, and reinforcing bars (diameter 1 cm × 80 cm) are arranged at intervals of 20 cm. The mortar was further cast so as to have a total height of 6 cm. After leaving at room temperature for 168 hours, the cured molding plate was released from the mold, and the tape was removed. As a result, only the portion in contact with the tape was washed out at a depth of 2 to 3 cm, and the washout surface having a width of 5 cm having a natural color of sand and a rough surface formed by sand particles was 10 c.
Clearly formed at m intervals.

Example 2 A monomer formulation was prepared by adding 3136 g (32.0 g) of maleic anhydride.
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. This polymerizable composition was poured into a stainless steel vat (25 cm × 40 cm × 5 cm) so as to have a height of 2 cm, and was placed in a furnace at 120 ° C. for 1 hour.
The composition was cured by heating for 5 minutes. The cured product is cooled to room temperature, coarsely pulverized by a crusher, further pulverized by a freeze pulverizer, and classified to have a particle size of 100 μm or less (average particle size of about 60 μm).
μm) of a powdery resin.

In 1200 ml of water, 500 g of the above powdery resin, 0.5 g of polyoxyethylene lauryl ether as a dispersant, and sodium polyacrylate 3 as an adhesive were used.
0 g and 150 g of polyvinyl acetate emulsion (solid content 30% by weight) were added, and the mixture was vigorously stirred with a stirrer.
A resin suspension for delaying cement setting was obtained. The resulting suspension was applied to the bottom of the wooden formwork used in Example 1 by spraying to a width of 10 cm so that the thickness after drying was about 200 μm, and allowed to dry at room temperature for 24 hours. . The mortar used in Example 1 was poured into a mold at a height of 5 cm,
The reinforcing bars used in Example 1 were arranged at 0 cm intervals, and mortar was further cast so as to have a total height of 10 cm. After curing in the same manner as in Example 1, the concrete molded product was released from the mold and washed out, and sand and cement were washed out only at the application site of the suspension at a depth of about 2 mm. At the washed-out portion after drying, a shallow groove-like rough surface where the natural color of sand and the sand particles were exposed was formed. In addition, the non-applied portion of the suspension was cured, and the curing retarding effect was not exerted.

Example 3 The monomer formulation was changed to 3603 g of maleic anhydride (31.1 g).
Mol) and 100 parts by weight of an unsaturated polyester (weight average molecular weight: 1950) obtained in the same manner as in Example 1 except that glycerin was changed to 2,674 g (29.1 mol). Of organic peroxide (Nippon Oil & Fats Co., Ltd .; Perbutyl O) 3 parts by weight with respect to 100 parts by weight of
To prepare a polymerizable composition. This polymerizable composition is put on a stainless steel vat (25 cm × 40 cm × 5 cm)
At a height of 2 cm, and in a furnace at 120 ° C.
For 15 minutes to cure. The cured product is cooled to room temperature, coarsely pulverized by a crusher, further pulverized by a freeze pulverizer, and classified to have a particle size of 100 μm or less (average particle size of about 6 μm).
0 μm).

In 1200 ml of water, 500 g of the powdery resin, 0.5 g of polyoxyethylene lauryl ether as a dispersant, and sodium polyacrylate 3 as an adhesive were used.
0 g and 150 g of polyvinyl acetate emulsion (solid content 30% by weight) were added, and the mixture was vigorously stirred with a stirrer.
A resin suspension for delaying cement setting was obtained.

Form (60 cm × 55 cm × (depth) 10
cm), the mortar used in Example 1 was cast at a height of 5 cm, reinforcing bars were arranged at intervals of 20 cm, and the mortar was further cast so as to have a total height of 10 cm. The above-mentioned resin suspension for cement setting delay was sprayed on the surface of the mortar that was cast by spraying (100 g / m2 as a polymer).
² ). Curing treatment was performed at 50 ° C. for 24 hours, and after leaving at room temperature for further 24 hours, the mold was released. After demolding, the uncured mortar composition and remaining polymer particles on the hardened concrete surface were removed with a brush, and the concrete surface was washed with a broom while applying pressure water. A clean wash surface was formed.

Example 4 Concrete was poured into the ground with a width of 2 m on the ground, and a part of the surface was sprayed with the resin suspension for cement setting delay obtained by the same operation as in Example 3 by spraying. Depending on the device,
It was sprayed at a rate of about 100 g (in terms of polymer) per 1 m ² . After being left at room temperature for 3 days, the remaining polymer particles and the like were suctioned and removed by a vacuum cleaner while brushing. As a result, a washout surface having an uneven shape was formed on the concrete surface where the suspension was sprayed. .
When the vehicle was driven on the road thus obtained under rainy weather, tire slip was significantly suppressed in a portion where the uneven shape was formed as compared with other portions.

Example 5 The resin suspension for cement setting retardation obtained by the same operation as in Example 2 was applied to the entire bottom surface of the wooden form used in Example 1 to a thickness of about 100 μm after drying. And dried at room temperature for 24 hours to form a cement setting retardation layer composed of polymer particles. On this curing delay layer, a square tile (10 cm × 10 cm × (thickness) 8
cm) and joint bars (squares having a cross section of 10 mm × 10 mm) were alternately arranged, and the mortar used in Example 1 was cast. After being left to cure at room temperature for 168 hours, the concrete molded product was released from the mold, the remaining polymer particles and the like were removed with a broom, and the tile surface was washed while applying pressurized water. As a result, a surface decorative concrete plate having an extremely beautiful appearance was obtained. It should be noted that the deposits on the tile surface could be removed smoothly only by washing with water, and the removal operation using a wire brush, a spatula or the like was unnecessary.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C08F 290/06 MSN C08F 290/06 MSN C08G 63/52 NPD C08G 63/52 NPD E04F 13/02 0231 −2E E04F 13 / 02F // C04B 103: 24

Claims (15)

[Claims] 1. A resin suspension for delaying cement setting, comprising polymer particles capable of exhibiting the ability to delay cement setting by hydrolysis. 2. The resin suspension for cement setting retardation according to claim 1, wherein the polymer constituting the polymer particles is an unsaturated polyester. 3. 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. The resin suspension for cement setting retardation according to claim 2, which is an unsaturated polyester obtained by reaction with a polyol component containing an alcohol or a condensate thereof. 4. The method of claim 1, wherein the unsaturated polycarboxylic acid is maleic acid,
4. The resin suspension for cement setting retardation according to claim 3, which is maleic anhydride, fumaric acid or a derivative thereof. 5. The resin suspension for cement setting retardation according to claim 3, wherein the polycarboxylic acid component further contains an aromatic polycarboxylic acid. 6. The resin suspension for cement setting retardation according to claim 3, wherein the polyhydric alcohol is ethylene glycol, propylene glycol, glycerin or a condensate thereof. 7. The resin suspension according to claim 2, wherein the unsaturated polyester has a weight average molecular weight of 300 to 100,000. 8. The resin suspension for cement setting retardation according to claim 2, wherein the unsaturated polyester is a cured product by crosslinking. 9. The resin suspension for cement setting retardation according to claim 8, wherein the cured product is a cured product of a polymerizable composition containing an unsaturated polyester, a polymerizable vinyl monomer and a polymerization initiator. 10. A method for producing a concrete structure having a scouring surface formed on a surface thereof, wherein the cement-setting retarding resin suspension or the suspension according to claim 1 is applied to the surface of an inorganic curable composition. After contacting the resin composition obtained by removing the solvent from the and curing the inorganic curable composition, the concrete structure to remove the non-cured inorganic curable composition from the surface of the resulting concrete cured product Manufacturing method. 11. A cement comprising polymer particles capable of exhibiting cement setting delay ability by hydrolysis by applying or impregnating the surface of the base sheet with the resin suspension for cement setting delay according to claim 1. Forming a curing retardation layer,
The obtained sheet is disposed in a mold so that the cement setting retardation layer becomes the surface, and after the inorganic curable composition is cast and cured, the mold and the sheet are removed. The method for producing a concrete structure according to claim 10, wherein the uncured inorganic curable composition is removed from the surface of the cured concrete product. 12. A cement hardening composed of polymer particles capable of expressing a cement hardening delaying ability by hydrolysis by applying or impregnating the resin suspension for cement hardening delay according to claim 1 to a bottom plate of a mold. The method according to claim 10, wherein after forming the retardation layer, pouring the inorganic curable composition and performing a curing treatment, removing the uncured inorganic curable composition from the surface of the obtained concrete cured product. Manufacturing method of concrete structure. 13. An inorganic curable composition is poured into a mold,
The resin suspension for cement setting delay according to claim 1 is sprayed on the surface thereof, and after the inorganic curable composition is subjected to the curing treatment, the mold is removed, and non-cured inorganic curing is performed from the surface of the obtained concrete cured product. The method for producing a concrete structure according to claim 10, wherein the conductive composition is removed. 14. An inorganic curable composition is poured over a predetermined width and a predetermined distance on the ground, and the resin suspension for cement setting delay according to claim 1 is sprayed on the surface thereof. The method for producing a concrete structure according to claim 10, wherein after the object is cured, the uncured inorganic curable composition is removed from the surface to obtain a concrete pavement road. 15. A method for producing a surface-decorated concrete structure integrated with a decorative material, comprising applying or impregnating the resin suspension for cement setting retardation according to claim 1 to a surface of a base, and subjecting the suspension to hydrolysis. A cement setting delay layer composed of polymer particles capable of expressing cement setting delay ability was formed, a decorative material was disposed on the cement setting delay layer, and an inorganic setting composition was cast and cured. Then, a method for producing a concrete structure, in which the mold is removed and the uncured inorganic curable composition is removed.