JPH09183643A - Cement hardening retarder and cement hardening delaying sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a pattern or a washed-out surface on the surface of a concrete product by setting a mortar composition and washing the hardened surface. SOLUTION: The pattern or the washed-out surface is formed on the surface of the concrete product by using a polyester as a cement hardening retarder, in which its main chain is obtained by the reaction of a polyvalent carbonic acid component containing a 2-6C polyvalent carbonic acid with a polyol component containing a 2-4C polyvalent alcohol or its condensed product to suppress the hardening of the cement. The unsaturated polyester can be used as a polymerizable composition containing a polymerization initiator and a polymerizable vinyl monomer, etc. The hardening retarder may be a granular body as a cured body of the unsaturated polyester. The composition containing the hardening retarder and an adhesive agent is coated on a base sheet or impregnated thereinto, thus the hardening delaying sheet may be formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cement setting retarder useful for delaying the hardening of the surface of a curable composition containing cement, and a cement setting delay sheet 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 hardening of mortar and 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, magnesium fluorosilicate, and polyhydroxy compounds (sugar, alcohol, Organic curing retarders such as keto acids such as methyl cellulose, ethyl cellulose, polyvinyl alcohol, dextrin), sodium polyacrylate, oxycarboxylate, lignin sulfonate, gluconic acid or a salt thereof, pyruvic acid and α-ketoglutaric acid. Is 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. It is often practiced to decorate the surface 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 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, and mass production or application to large buildings is an unsuitable technique. 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, the tile is placed on a form on which concrete is cast, the mortar is poured into the form, cured, then removed, and the adhesive sheet is removed to expose the tile on the surface. After that, the tiles are constructed by wrapping around the tile surface, removing the hardened cement, and finishing the surface.
This surface finish 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 work to remove the hardened cement adhering to the tile is
This is time-consuming and troublesome, and not only increases the tile construction cost, but also causes the tile surface to be damaged by the hardened cement removal operation.

[0003] In order to solve such a problem, a cement setting retarder, which is a kind of concrete admixture, is applied to prevent hardening of only the surface layer of concrete, thereby processing the surface of a concrete product or treating the surface of a concrete product. It has been proposed to form a pattern. 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. A method has been proposed in which uncured mortar on the surface is washed away to expose the aggregate and obtain a natural texture. JP-A-63-216
No. 703 discloses a process of cutting a paper pattern in which a curing retardant is impregnated into paper to produce a paper pattern corresponding to a pattern such as a predetermined character or figure, and bonding the paper pattern to a predetermined portion of the inner surface of the mold. Process, placing mortar in the formwork,
A predetermined uneven pattern is formed on the surface of the concrete product through a process of curing, a process of taking out the concrete product by disassembling the formwork, and a process of cleaning a pattern portion of the concrete product. JP-A-61-202803 discloses a method in which a tile or the like is attached to paper coated with the cement setting retarder, set in a mold, and washed out in the same manner as described above. JP-A-5-38711 and JP-A-5-50411 disclose super retarders,
A mixture containing a tackifier, a bulking agent, and a white pigment is adhered to the inner surface of the mold, mortar or concrete is poured, cured and demolded, and a cement paste of a cement product on a contact surface with the mold is used. A method for washing and finishing the surface of a cement product is disclosed. However, conventional setting retarders that suppress the hydration mechanism of cement have high solubility in water and dissolve in moisture 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 accurately form particularly complicated decorations such as decorative characters and figures on a predetermined portion of the surface of a concrete molded product or a building.

Japanese Patent Application Laid-Open No. Hei 3-224953 discloses that a concrete non-hardening agent is applied to the inner wall of a formwork, decorative materials such as tiles and stones are arranged via joint bars, and a reinforcing bar is provided at a predetermined height. After assembling, casting concrete and curing,
A method for manufacturing a concrete block integrated with a decorative material by removing the mold and washing the surface of the concrete product with water is disclosed. This document discloses that a composition containing an alkali swelling agent, a superabsorbent polymer, a water-absorbing monomer, and a curing agent is cured as a concrete non-hardening agent to form a cured film containing a higher aqueous polymer. 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 poured and cured, and then removed from the surface of the concrete product. A method is disclosed for removing uncured coating material and uncured portions of concrete by washing with water to produce a surface-decorated concrete product. This prior art document describes forming the uncured coating material layer with a mixture of an alkali swelling material such as polyester, polyvinyl alcohol, and polyvinyl acetal and a super absorbent polymer. However, according to the methods described in these prior art documents, the decorative material provided in the mold is displaced by the casting of the mortar composition or the concrete non-hardening agent is washed away, so that the predetermined material of the concrete product is lost. It is difficult to form a washout surface or a pattern at a site. In addition, since it is necessary to apply an uncured coating material to the surface of the decorative material, it is difficult to improve workability and productivity of concrete products. In addition, Japanese Unexamined Patent Publication (Kokai) No. 3-175003 describes that the non-hardened concrete material may be in a sheet form. However, since the concrete non-hardening material is composed of a mixture of an alkali swelling material and a super absorbent polymer, it is difficult to form a sheet. Further, in order to delay the setting of the cement, a superabsorbent polymer is required in addition to the alkali swelling material, and details of polyester described as an example of the alkali swelling agent are not disclosed.

[0005]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a cement setting retarder having a high ability to inhibit the setting of cement, despite its low solubility in water. Another object of the present invention is to provide a cement setting retarder which is useful for suppressing outflow due to moisture and forming a pattern or a washout surface on a concrete product with high accuracy. Still another object of the present invention is that, even when the mortar composition is cast, it is possible to suppress the flow of the curing retarder, and also to uniformly suppress the curing at the contact surface with the mortar composition, and to apply it to the surface of the concrete product. An object of the present invention is to provide a curing retardation sheet capable of forming a pattern and a washout surface with high accuracy. Another object of the present invention is to provide a sheet useful for decorating the surface with a decorative material or the like while suppressing damage and obtaining a decorative finish concrete product. Still another object of the present invention is to provide a curing retardation sheet that can easily and efficiently form a pattern and a washout surface on the surface of a concrete product. Another object of the present invention is to provide a hardening delay sheet which can be easily formed even on a surface of a concrete product even if it has a complicated pattern, and can enhance decorativeness.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, (1) increasing the molecular weight of a specific polycarboxylic acid component and a polyhydric alcohol component by an esterification reaction. When polyester is used, insolubility in water can be maintained, and when mortar or concrete is cast, polyester is gradually and effectively used due to strong alkalinity, although it does not originally have the ability to retard hardening of cement. (2) a setting retarder having the ability to retard the setting of cement (the ability to control), as the curing of the cement progresses, the hydrolysis product extremely effectively expresses the setting delay of the cement. It has been found that when the sheet is held on a sheet, a pattern and a washout surface can be accurately formed on the surface of the concrete product, and the present invention has been completed.

That is, the cement setting retarder of the present invention comprises a polyvalent carboxylic acid component having a main chain containing a polyvalent carboxylic acid having 2 to 6 carbon atoms or a derivative thereof, and a polyhydric alcohol having 2 to 4 carbon atoms or a polyhydric alcohol having the same. It is composed of a polyester obtained by a reaction with a polyol component containing a condensate. The polyvalent carboxylic acid is a saturated dicarboxylic acid having a main chain of 2 to 5 carbon atoms,
An unsaturated dicarboxylic acid having an ethylenically unsaturated bond such as maleic acid or maleic anhydride and having a main chain of 4 to 6 carbon atoms may be used. The polycarboxylic acid component may further contain an aromatic dicarboxylic acid such as phthalic acid or a derivative thereof. The main repeating unit of the polyester,
It may be composed of a repeating unit having 4 to 9 carbon atoms. The cement setting retarder is a cured product of an unsaturated polyester, for example, (i) a polymerizable composition containing an unsaturated polyester and a polymerization initiator, (ii) an unsaturated polyester, a polymerizable vinyl monomer, and a polymerization initiator. And a cured product such as a polymerizable composition containing the same. The cured product may be used as a powder.

In the cement setting retardation sheet of the present invention, a polycarboxylic acid component containing a polycarboxylic acid having 2 to 6 carbon atoms or a derivative thereof, a polyhydric alcohol having 2 to 4 carbon atoms or a condensate thereof The composition containing the cement setting retarder composed of the polyester obtained by the reaction with the polyol component containing is held on the base sheet. In addition,
In the present specification, “sheet” means a two-dimensional structure regardless of thickness, and is used to include a film. The term “polycarboxylic acid derivative” is used to include an acid anhydride and a lower alkyl ester of a polycarboxylic acid (for example, a removable C _1-4 alkyl ester such as a methyl ester or an ethyl ester). In addition, "adhesive or adhesive" is collectively referred to as "adhesive", "adhesive layer or adhesive layer" is collectively referred to as "adhesive layer", and "adhesive or adhesive" is referred to as "adhesive". Sex ". Further, unless otherwise specified, “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”.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION

[Cement setting retarder of the present invention] The cement setting retarder of the present invention is obtained by reacting a polyvalent carboxylic acid component containing a polyvalent carboxylic acid or a derivative thereof with a polyol component containing a polyhydric alcohol or a condensate thereof. Made of polyester. Polyvalent carboxylic acids have the formula HOOCR
¹ COOH (wherein R ¹ is a direct bond between both carboxyl groups or a main chain is an alkylene group having 1 to 4 carbon atoms), a saturated polycarboxylic acid represented by the formula HOOCR ² COOH (R ² is a main chain having carbon atoms And an unsaturated hydrocarbon group having a polymerizable unsaturated bond such as an ethylenic unsaturated bond represented by the formula (2) to (4), which represents an aliphatic hydrocarbon group having an unsaturated double bond. In the above formula, the alkylene group of R ^{1 and} the unsaturated hydrocarbon group of R ² may be branched, but the number of carbon atoms of a substituent such as an alkyl group branched from the main chain is the same as that of R ¹ and R ¹ Not included in main chain carbon number ² . Hereinafter, unless otherwise specified, the carbon number of the polyvalent carboxylic acid means the carbon number of the main chain.

Examples of the polyvalent carboxylic acid in which R ¹ is a direct bond or an alkylene group having 1 to 4 carbon atoms in the main chain (that is, having 2 to 6 carbon atoms in the main chain including a carbon atom in the carboxyl group) include: Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and the like, wherein R ² is an unsaturated aliphatic hydrocarbon group having 2 to 4 carbon atoms in the main chain (that is, a main group including carbon atoms of carboxyl group). Unsaturated polycarboxylic acids having a chain of an unsaturated hydrocarbon group having 4 to 6 carbon atoms include aliphatic dicarboxylic acids (eg, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid). acid,
Citraconic anhydride, mesaconic anhydride, etc.). 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 polycarboxylic acid, an aliphatic polycarboxylic acid (eg, azelaic acid, sebacic acid, etc.), an aromatic polycarboxylic acid (eg, phthalic acid, phthalic anhydride, terephthalic acid). , Isophthalic acid, trimellitic acid, pyromellitic acid, etc.). In particular, when a polyvalent carboxylic acid component containing an aromatic dicarboxylic acid or a derivative thereof selected from phthalic acid, terephthalic acid, isophthalic acid or a derivative thereof is used, the strength of the saturated or unsaturated polyester,
It is useful for adjusting properties such as elongation, flexibility, flexibility, and water resistance. The content of the aromatic polycarboxylic acid relative to the entire polyester is, for example, 0.1 to 30% by weight, preferably 0.1 to 20% by weight (for example, 1 to 15% by weight), and more preferably 0.1 to 15% by weight. 10% by weight (for example,
2 to 10% by weight).

Preferred polyvalent carboxylic acids include (1) a dicarboxylic acid component containing a saturated or unsaturated aliphatic dicarboxylic acid having 2 to 6 carbon atoms or a derivative thereof (particularly, a saturated aliphatic dicarboxylic acid having 2 to 5 carbon atoms, Or a dicarboxylic acid component containing at least maleic acid or a derivative thereof), or (2) a saturated or unsaturated aliphatic dicarboxylic acid having 2 to 6 carbon atoms or a derivative thereof, and phthalic acid, terephthalic acid, and isophthalic acid. A dicarboxylic acid component containing at least one aromatic dicarboxylic acid or a derivative thereof is included. Particularly preferred polyvalent carboxylic acid components include (3) a saturated dicarboxylic acid having about 2 to 4 carbon atoms or a derivative thereof;
Or 5 unsaturated dicarboxylic acids or derivatives thereof (especially maleic acid or maleic anhydride), (5) the saturated dicarboxylic acids (3) and / or unsaturated dicarboxylic acids (4) (especially maleic acid or maleic anhydride). , An aromatic dicarboxylic acid or a derivative thereof (particularly, an aromatic C ₈ dicarboxylic acid or a derivative thereof).

The polyol component includes polyhydric alcohols having 2 to 4 carbon atoms, for example, diols (for example, C _2-4 such as ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, tetramethylene glycol, etc.). alkylene glycol), a polyoxyalkylene glycol is a condensation product of C _2-4 alkylene glycols, for example, dioxyethylene glycol, trioxyethylene glycol, polyoxyethylene glycol (hereinafter, unless otherwise specified, and to simply polyethylene glycol May be collectively referred to), dioxypropylene glycol, trioxypropylene glycol, polyoxypropylene glycol (hereinafter, unless otherwise specified, these may be simply referred to as polypropylene glycol). Such as polyoxytetramethylene glycol; polyols (e.g., glycerol, diglycerol, polyglycerol) contains. 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, and polyoxypropylene glycol. , And glycerin. The polyhydric alcohol often includes a diol component, particularly a diol component composed of an aliphatic diol having 2 to 4 carbon atoms 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), and when polyethylene glycol is used, the weight average molecular weight is 300 or less. Often. Glycol components including propylene glycol and polypropylene glycol are useful for imparting flexibility and hydrophilicity, and are useful for enhancing the solubility with polymerizable monomers such as styrene and acrylic monomers.

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

The main repeating unit of the polyester,-(R
^a COOR ^b OCO) — (wherein ^Ra represents a residue of a polycarboxylic acid and R ^b represents a residue of a polyhydric alcohol) is a repeating unit having 4 to 9 carbon atoms (that is, a polyvalent carboxylic acid and (In which the total carbon number of the polyhydric alcohol is 4 to 9). Of these polyesters, unsaturated polyesters, particularly unsaturated polyesters containing maleic acid or maleic anhydride as a polyvalent carboxylic 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 25000), preferably 300 to 50,000.
000 (e.g., 500 to 15000), and more preferably in the range of about 500 to 20,000. The unsaturated polyester has a weight average molecular weight of 300 to
100,000, preferably 300 to 50,000, more preferably about 500 to 10,000, and a weight average molecular weight of 300 to 5,000 (for example, 500 to 5,000).
Particularly, it is often about 500 to 2500. The molecular weight is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography.

The polyester may be oily or solid. The oily polyester is dissolved as it is, and the solid polyester is dissolved in an organic solvent and applied or impregnated on a base sheet (for example, a nonporous sheet such as a plastic sheet or metal foil, a porous sheet such as paper or nonwoven fabric) or the like. It can be applied to the inner bottom surface or the inner side wall of a mold made of wood or the like by brush or spray. Further, the solid polyester may be used as a granular material, or may be heated and melted and applied or impregnated on a base sheet.

A polyester such as an unsaturated polyester can be obtained by a conventional method, for example, by condensing a polycarboxylic 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 cement setting retarder of the present invention may be composed of the polyester described above, and when the polyester is an unsaturated polyester, it may be composed of a cured product of the unsaturated polyester. 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. Such a polymerizable composition (i)
Even if the unsaturated polyester constituting the cement setting retarder has a low molecular weight such as an oil that is difficult to handle, it is cured by self-crosslinking with a polymerization initiator and used as a powdery cement setting retarder. Performance can be improved. Further, the polymerizable composition (i) containing a low-molecular unsaturated polyester, for example, an unsaturated polyester having a weight-average molecular weight of about 300 to 5,000 has a relatively low viscosity and a high coating or impregnating property with respect to a base sheet. . Further, the sheet can be held as a crosslinked composition by curing.

The cured product of the unsaturated polyester may be a cured product of the polymerizable composition (ii) containing the unsaturated polyester, a polymerizable vinyl monomer (reactive diluent) and the polymerization initiator. Examples of the polymerizable vinyl monomer include styrene-based monomers such as styrene, α-methylstyrene, and vinyltoluene; and alkyl groups having 1 carbon atom such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate. Alkyl (meth) acrylate of about 20 to 20 (particularly 1 to 10 carbon atoms), 2
-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acrylic acid, glycidyl (meth) acrylate, and other functional groups (hydroxyl, carboxyl, glycidyl) And esters of (meth) acrylic acid with the polyhydric alcohol (eg, polyethylene glycol) (eg, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate). 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 styrenic monomers, acrylic monomers and methacrylic monomers. The amount of the polymerizable vinyl monomer to be used is, depending on the molecular weight of the unsaturated polyester, within a range that does not impair the curing retarding ability and 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 5 to 200 parts by weight (for example, 5 to 100 parts by weight).
The range may be about 30 parts by weight. Even if the polymerizable composition (ii) is a solid or viscous unsaturated polyester, it can be easily taken out of the reaction apparatus by adding a polymerizable vinyl monomer, and the unsaturated polyester is difficult to handle. Or, even if it is viscous, it can be crosslinked and cured, and by using it as a powdery cement setting retarder, handleability can be improved. Further, the polymerizable composition (ii) can be held as a cross-linked composition by coating or impregnating the base sheet and curing it.

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; β-diketones such as acetylacetone and ethyl acetoacetate; aromatic tertiary amines; and mercaptos. 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.
ppm (for example, 10 to 100 ppm), and may be about 30 to 50 ppm.

The curing (cross-linking) of the unsaturated polyester can be carried out 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 carry out the curing at a temperature of about 60 to 200 ° C. It is advantageous.

As described above, the cement setting retarder of the present invention can be composed of an oily or solid (for example, powdery) saturated polyester or unsaturated polyester. The cured product of the unsaturated polyester as the curing retarder can be used as a granular material, and may be held on the base sheet as a crosslinked composition. The particle size of the granular saturated polyester and unsaturated polyester, and the granular cured product is not particularly limited,
For example, the average particle diameter can be appropriately selected from the range of 0.1 to 1000 μm, preferably about 0.1 to 500 μm.
The cement setting retarder of the present invention may be used in combination with another setting retarder. Further, the cement setting retarder of the present invention may be various additives depending on the type of polyester, for example, pigments, coloring agents such as dyes, ultraviolet absorbers, stabilizers such as antioxidants, polymerization inhibitors, plasticizers. Agents, defoamers, emulsifiers, hydrolysis accelerators, inorganic salts, metal oxides, fillers such as sand, and the like.

The polyester itself constituting the cement setting retarder of the present invention has little or no setting retarding ability to cement, and even if it has the setting retarding ability, it is extremely small. Unlike conventional curing retarders, they hardly dissolve in water and hardly flow with bleed water from mortar or concrete. However, the ester bond of the polyester is hydrolyzed due to the strong alkalinity of the uncured mortar or concrete, and a carboxyl group and a hydroxyl group useful for retarding the curing are released. This rate of hydrolysis increases as the moisture in the mortar or concrete is used to harden the cement, and is maximized by the heat of the concrete during curing, and in the case of heat curing, by the heating, and the free carboxyl groups And the hydroxyl group synergistically exhibit a large effect delay ability. On the other hand, concrete at the stage where the curing retarding ability is developed is still in an uncured state, but has no fluidity, and even if the curing retarding component is liberated due to hydrolysis of the polyester, it will no longer dissolve and move in the water of lead water. Nor. Therefore, the curing retarding ability can be exhibited only at a desired site, and a pattern such as a character or a picture can be formed by washing out the cement after curing.

Although the cement setting retarder of the present invention is useful for forming a desired pattern with high accuracy by washing out, it is used in the same manner as a conventional setting retarder, for example, for a long period of fresh concrete in summer. May be added to mortar or concrete in order to suppress hardening over a long period of time and to alleviate stress due to temperature in large concrete structures.

[Cement Setting Delay Sheet of the Present Invention] The cement setting delay sheet of the present invention comprises (A1) a composition containing a cement setting delay agent composed of the saturated or unsaturated polyester, which is held on a base sheet. Curing retardation sheet, and (A2) a curing retardation sheet in which a curing retardation layer containing a concrete curing retardant and an adhesive or an adhesive is formed on the surface of a base sheet. [Cement Setting Delay Sheet (A1)] In the cement setting delay sheet (A1), the composition containing the saturated or unsaturated polyester is held on a base sheet. When the polyester is oily, the composition may be used as it is. Further, the polyester may be heated and melted to be applied or impregnated on the base sheet, or may be used by dissolving it in an organic solvent regardless of the form (for example, solid). Examples of the organic solvent include alcohols such as ethanol and isopropanol, aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, halogens such as dichloromethane and dichloroethane. Examples thereof include hydrocarbons, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, ethers such as diethyl ether and tetrahydrofuran, and mixed solvents thereof.

When the polyester is an unsaturated polyester, the polymerizable composition described above, that is, the polymerizable composition (i) containing the unsaturated polyester and the polymerization initiator, the unsaturated polyester, the polymerizable monomer and the polymerization initiator Or a polymerizable composition (iii) obtained by adding a polymerization accelerator to these compositions (i) and (ii).

Furthermore, when the polyester is in the form of powder (particularly when the powder is a cured product of an unsaturated polyester), it may be used as a composition containing the polyester powder and a pressure-sensitive 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. And acrylic elastomers, polyester elastomers, and the like. These may be emulsion-type adhesives or solvent-type adhesives. Also, water-soluble viscous substances, for example, polyvinyl alcohol, polyacrylic acid, polyacrylamide, methylcellulose, hydroxyethylcellulose, synthetic water-soluble polymers such as carboxymethylcellulose, locust bean gum, guar gum, gum arabic, gum tragacanth, 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. Further, the pressure-sensitive adhesive composition may be used in combination with a tackifier (for example, a hydrocarbon-based resin such as a petroleum resin, a terpene-based resin, or a dicyclopentadiene-based resin, or a rosin derivative). The pressure-sensitive adhesive or the adhesive composition may contain an inorganic filler or the like in order to adjust the adhesive strength. In a composition comprising a polyester powder and a pressure-sensitive adhesive or adhesive,
The content of the pressure-sensitive adhesive or the adhesive may be within a range that does not impair the curing delay property, the pressure-sensitive adhesive property or the adhesive property, and for example, is 10 to 2000 parts by weight, preferably 50 to The amount is 1000 parts by weight, more preferably about 100 to 500 parts by weight.

The base sheet includes, for example, non-porous sheets such as plastic sheets and metal foils, and porous sheets such as paper, woven fabric and non-woven fabric. Among the substrate sheets, preferred non-porous sheets include plastic sheets, and porous sheets include plastic nonwoven fabrics. The polymer constituting the base sheet is not particularly limited. For example, olefin polymers such as polyethylene and polypropylene; polyesters such as polyethylene terephthalate and polybutylene terephthalate (especially polyalkylene terephthalate); ethylene-vinyl acetate copolymer; 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. Further, the base sheet may be a sheet having improved hand-cutting property and dimensional stability.

The base sheet may be a single sheet or a composite sheet in which a plurality of layers are laminated, for example, one or both sides of a cloth woven with fibers such as polyethylene fibers, and the sheet of polyethylene or the like. May be a laminated sheet or the like. The base sheet such as a plastic sheet may be an unstretched sheet or a uniaxially 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, in order to enhance the adhesiveness with the composition containing the polyester. The surface tension of the surface-treated substrate sheet is often about 40 dyn / cm or more. The thickness of the base sheet can be selected within a range that does not impair workability, mechanical strength, and the like.
0 μm, preferably 20 to 400 μm, more preferably about 30 to 300 μm, and often about 50 to 300 μm.

The form of holding the polyester (preferably unsaturated polyester) on the base sheet is not particularly limited, and can be selected according to the type of the composition containing the polyester. For example, the polyester may be retained by applying or impregnating the composition containing the saturated or unsaturated polyester to a base sheet,
In the polymerizable compositions (i) to (iii), the base sheet may be coated or impregnated, and then cured or cross-linked by heating to hold the cross-linked composition. Polymerization or crosslinking of the polymerizable composition may be performed at room temperature,
° C or more (for example, 100 to 200 ° C), preferably 10 ° C
0 to 170 ° C (for example, 100 to 150 ° C), particularly 12
It is often performed at a temperature of about 0 to 150 ° C.

Further, in the case of the composition containing the powdery and granular polyester and the pressure-sensitive adhesive or the adhesive, the base sheet may be coated or impregnated to hold the composition in the same manner as described above. further,
In the case of using the particulate polyester, the particulate polyester may be held on the pressure-sensitive adhesive layer or the adhesive layer formed on the surface of the base sheet by adhering the polyester by spraying or the like. The granular polyester may be obtained, for example, by cooling and pulverizing the polyester according to the form of the polyester. The thickness of the pressure-sensitive adhesive layer having the powdery polyester is, for example, 30 to 500 μm, preferably 100 to 500 μm, and more preferably 150 to 300 μm.
μm, and often about 200 to 250 μm.

The cement setting delay sheet also includes (A2) a setting delay sheet in which a setting delay layer containing a concrete delay setting agent and an adhesive or an adhesive is formed on the surface of a base sheet. In the cement setting delay sheet (A2), a setting delay layer containing a concrete setting delay agent and an adhesive or an adhesive is formed on the surface of the base material sheet. Other set retarders can also be used. As the base sheet, the pressure-sensitive adhesive or the adhesive, the same base sheet, pressure-sensitive adhesive or adhesive as described above can be used. The type of the curing retarder other than the polyester is not particularly limited as long as it is a curing retarder or a setting retarder that reduces the curing speed of the cement, and an inorganic or organic curing retarder can be used. Inorganic cure retarders include phosphoric acid, boric acid or salts thereof, hexafluorosilicate, and the like. Examples of the organic curing retarder include a phosphonic acid compound having a phosphonic group PO ₃ H ₂ and a non-phosphonic acid-based compound as shown below. Phosphonic acid-based curing retarders aminodi (methylenephosphonic acid), aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-
Diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), and salts thereof.

Examples of the salt include salts with alkali metals such as ammonia, sodium and potassium, and alkaline earth metals such as calcium, magnesium and barium. Examples of the salt of the phosphonic acid compound include aminotri (methylenephosphonic acid) pentasodium salt, 1-hydroxyethylidene-1,1-diphosphonic acid tetrasodium salt, ethylenediaminetetra (methylenephosphonic acid) calcium sodium salt, hexamethylenediamine Potassium tetra (methylene phosphonate), sodium diethylenetriaminepenta (methylene phosphonate) and the like are included.

Non-phosphonic acid-based curing retarders Oxycarboxylic acids such as glycolic acid, lactic acid, malic acid, tartaric acid, citric acid and gluconic acid or salts thereof: saturated polycarboxylic acids such as oxalic acid and malonic acid, fumaric acid, Unsaturated polycarboxylic acids such as itaconic acid, polycarboxylic acids such as glucoheptanonic acid or salts thereof; polymaleic acid, polyfumaric acid, styrene-maleic acid copolymer, polyacrylic acid, polymethacrylic acid, styrene- ( Meta)
Acrylic acid copolymer, (meth) acrylic acid ester-
(Meth) acrylic acid copolymer, ethylene sulfonic acid-acrylic acid copolymer, etc., a monomer having a carboxyl group alone or copolymer or a salt thereof (preferably a low molecular weight polymer or a salt thereof); an antioxidant (for example, , Ascorbic acid, isoascorbic acid, etc.); polymers such as polyhydroxysilanes, polyacrylamides (preferably low molecular weight polymers): carbohydrates (eg, polysaccharides such as sucrose, corn syrup, etc.);
Humic acid; ligninsulfonic acid or lignosulfonate (eg, calcium lignosulfonate) and the like.

Among these curing retarders, a phosphonic acid compound, an oxycarboxylic acid, a polyvalent carboxylic acid, a homo- or copolymer of a monomer having a carboxyl group, isoalcorbic acid, phosphoric acid, boric acid or a salt thereof And at least one component selected from the group consisting of polyhydroxysilane and hexafluorosilicate. As the curing retarder, a phosphonic acid compound, a hydroxycarboxylic acid, a polycarboxylic acid (polycarboxylic acid), isoascorbic acid or a salt thereof, and polyhydroxysilane are often used. Combinations with carboxylic acids are preferred. Such combinations include, for example, a combination of aminotri (methylenephosphonic acid) and citric acid. The ratio of the phosphonic acid compound to the hydroxycarboxylic acid is, for example, the former / latter = 1
00/25 to 500 (weight ratio), preferably 100/5
It is about 0 to 250 (weight ratio). Preferred curing retarders have an acidic group (for example, a phosphonic acid group, a carboxyl group, a sulfonic acid group, etc.) or a salt thereof, and are often water-soluble. One or more curing retarders can be used.

The amount of the concrete setting retarder used is:
5 to 1000 parts by weight, preferably 10 to 700 parts by weight, more preferably about 25 to 500 parts by weight, and 25 to 400 parts by weight (for example, 50 to 300 parts by weight) with respect to 100 parts by weight of the pressure-sensitive adhesive or the adhesive. ) In many cases. The composition containing the curing retarder and the pressure-sensitive adhesive or the adhesive may further contain the same organic solvent or additive as described above, if necessary. The cement setting retardation sheet (A2) can be obtained by applying a composition containing a setting retarder and a pressure-sensitive adhesive or an adhesive to a base sheet and drying the composition. In the curing retardation sheets (A1) and (A2), the composition containing the curing retardant may be applied to at least one surface of the base sheet.

The cement setting retardation sheet is (A3) a sheet made of a resin having a cement setting delaying ability (for example, the above-mentioned polyester such as unsaturated polyester), (A4)
It may be a sheet composed of a composition containing a cement setting retarder. In addition, the sheet constituted of (A3) the curing retardant resin may contain the curing retarder. Curing retardation sheet (A3) (A4), using a composition containing a curing retardation resin or a curing retarder and a resin having a sheet forming ability, a conventional molding method, for example, an extrusion molding method, a casting method, It can be formed by a calendar method or the like. Examples of the resin having a sheet forming ability include thermoplastic resins (for example, olefin polymers such as polyethylene and polypropylene; polyesters such as polyethylene terephthalate, polybutylene terephthalate, and poly (1,4-dimethylol-cyclohexane terephthalate); nylon 46, nylon 6,
Polyamides such as nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, etc .; polyvinyl acetate, ethylene-vinyl acetate (EVA) copolymer, vinyl acetate-vinyl versatate copolymer (VA-Veo)
Va) and other vinyl ester resins; saponified vinyl ester resins such as polyvinyl alcohol and ethylene-vinyl alcohol copolymer; ethylene-ethyl acrylate copolymer, ethylene- (meth) acrylic acid copolymer; Halogen-containing polymers such as vinyl chloride, vinyl chloride-vinyl acetate copolymer, vinylidene chloride-vinyl acetate copolymer, polychloroprene; acrylic polymers such as acrylic resin, styrene- (meth) acrylate copolymer; polystyrene Styrene-based polymers such as styrene-butadiene copolymer and styrene-butadiene-acrylonitrile copolymer; cellulose-based polymers such as methylcellulose, hydroxyethylcellulose and cellulose acetate; natural polymers and the like; thermosetting resins (for example, thermosetting) sex Acrylic resins, unsaturated polyester resins, vinyl ester resins, diallyl phthalate resins, epoxy resins, urea resins, phenol resins) can be exemplified. One or more of these resins can be used. In addition, as a resin having sheet-forming ability, a particularly preferable resin is often a hydrophilic resin (for example, a water-soluble or water-dispersible resin) or a hydrophilicized resin such as latex or emulsion.

In the curing retardation sheet (A4), the amount of the curing retardant is, for example, 5 parts by weight per 100 parts by weight of the resin.
To 1000 parts by weight, preferably 10 to 700 parts by weight, more preferably about 25 to 500 parts by weight,
It is often about 400 parts by weight (for example, 50 to 300 parts by weight).

The cement setting retardation sheet may be a sheet provided with tackiness or adhesiveness by mixing an adhesive or an adhesive into the (A5) sheet, or applying an adhesive or an adhesive to the sheet. In the sheet (A5) containing the adhesive,
The content of the pressure-sensitive adhesive is, for example, 10 to 500 parts by weight, preferably 25 to 400 parts by weight, more preferably about 50 to 300 parts by weight, based on 100 parts by weight of the curing retardant resin or the sheet moldable resin. In most cases, about 25 to 250 parts by weight. When the pressure-sensitive adhesive layer or the adhesive layer is formed by application, the pressure-sensitive adhesive layer or the adhesive layer is, for example, 0.1 to 150, depending on the type and the content of the curing retarder.
It can be formed to a thickness of about μm, 1 to 120 μm, or 10 to 100 μm.

Further, in the hardening delay sheet, the hardening delay layer of the hardening delay sheet (A2) is formed of a non-adhesive or non-adhesive hardening delay layer using a binder resin instead of an adhesive or an adhesive. The cured retardation sheet (A6) may be used. As the binder resin, for example, polyvinyl acetate, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, acrylic polymer, polystyrene, styrene-acrylate copolymer, polyester, polyacetal, Chlorinated polyolefins such as polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyamide, polyurethane, polycarbonate, chlorinated polypropylene, cellulosic polymers such as acetylcellulose, acetylbutylcellulose, ethylcellulose and nitrocellulose, elastomers (for example, natural Rubber, chlorinated rubber, hydrochloric acid rubber, butadiene rubber, isoprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, butyl rubber,
Chloroprene rubber, ethylene-propylene rubber, ethylene-propylene-nonconjugated diene rubber, acrylic rubber, chlorosulfonated polyethylene rubber, silicone rubber, urethane rubber, etc.). One or more of these binder resins can be used. The ratio of the curing retarder is, for example, 5 to 1000 parts by weight, preferably 10 to 700 parts by weight, more preferably about 25 to 500 parts by weight, based on 100 parts by weight of the binder resin,
It is often about 25 to 500 parts by weight (for example, 50 to 400 parts by weight).

Further, the curing retardation sheet may be a curing retardation sheet (A7) in which a pressure-sensitive adhesive layer or an adhesive layer is formed on the surface of the curing retardation sheets (A1) to (A6). When the sheets (A1) and (A2) have adhesiveness, the pressure-sensitive adhesive layer or the adhesive layer is not necessarily required. The pressure-sensitive adhesive layer or the adhesive layer may be formed on at least one surface of the sheet having the curing retarding ability. As the pressure-sensitive adhesive or adhesive, the same pressure-sensitive adhesive or adhesive as described above can be used. The thickness of the pressure-sensitive adhesive layer, while exhibiting adhesiveness to decorative materials such as tiles, can be selected in a range that does not impair the effect of suppressing the hardening of concrete, for example,
0.1 to 50 μm (for example, 1 to 50 μm), preferably 1 to 40 μm, more preferably about 2 to 30 μm, and often about 2 to 25 μm.

It is preferable that the pressure-sensitive adhesive layer is capable of leaching a curing retarder. The pressure-sensitive adhesive layer into which the curing retardant can be leached may be formed uniformly on the surface of the curing retardation sheet,
It may be formed unevenly. When the pressure-sensitive adhesive layer is formed uniformly, the thickness of the pressure-sensitive adhesive layer is, for example, 0.1 to 15 μm, preferably 1 to 10 μm, and more preferably 1 to 5 μm.
It is preferably a thin layer. When the pressure-sensitive adhesive layer is formed unevenly, the scattered pressure-sensitive adhesive layer may be formed as a regular pattern or an irregular pattern by a method such as coating or printing, regardless of the thickness. In addition,
When the surface of the curing retardation sheet has adhesiveness, the adhesive surface is often covered with a release sheet or other protective sheet or paper such as release paper.

Such a cured retardation sheet may be appropriately cut and used as a surface decoration sheet. For example, the cut delay sheet is fixed to the part of the inner wall of the formwork corresponding to the washing part of the concrete product by sticking, concrete is poured, after the concrete is hardened, the mold is released, and the part is removed. By washing off the uncured mortar on the surface of the corresponding concrete product, a decorative concrete product can be obtained. Also, since the polyester as a cement setting retarder is held on the base sheet, the setting retarder does not move even when the concrete is cast, and hardly dissolves in water,
It does not flow due to bleed water. Therefore, a decorative pattern such as a character or a pattern can be accurately and clearly applied to a desired surface portion of a concrete molded product or a building.

In the above-mentioned curing retardation sheet, a coating layer containing a curing retarder and a curing retardation layer (hereinafter sometimes simply referred to as a coating layer) may be peelable from the substrate sheet.
When the coating layer can be peeled from the base sheet, a predetermined portion or region is cut in accordance with a desired pattern or the like in the coating layer, peeled from the base sheet, and the sheet is disposed in a mold. A part corresponding to the non-cutting part of the surface of the concrete product is obtained by casting an inorganic curable composition (such as a mortar composition) and washing out the contact surface of the cured and cured concrete product with the sheet. A washout surface where a pattern, a graphic pattern, an aggregate, and the like are exposed can be formed. To make the coating layer peelable, the surface of the base sheet may be untreated, for example, wax,
It may be treated with a release agent such as higher fatty acid amide or silicone oil. The surface tension of the base sheet can be selected relatively in relation to the adhesive strength of the coating layer within a range that does not impair the releasability of the coating layer. The surface tension of the base sheet is, for example,
38 dyn / cm or less, preferably 20 to 38 dyn / cm
cm, more preferably about 25 to 36 dyn / cm.

The use of the curing retardation sheet to which the tackiness is imparted by the pressure-sensitive adhesive is useful in the production of concrete products having a pattern, a figure, or a washed surface formed on the surface, and concrete products integrally fixed with a decorative material. is there. That is, the sheet is laid in the mold with the adhesive surface facing upward, and the surface side of a plurality of decorative materials such as stones and tiles is arranged on the adhesive surface by adhesive, and the decorative material is positioned and fixed. Next, the inorganic curable composition is cast into a mold, cured by a conventional curing method such as curing, and the cured molded product is removed from the mold.
Then, the surface side of the cosmetic material (the side in contact with the sheet) is water,
By washing with pressurized water, jet flow, etc., the uncured composition adhering to the decorative material can be easily removed, and by removing the adhesive, the concrete product with the cleaned face decorative material bonded thereto ( Decorative blocks, precast concrete boards, etc.).
In the case where the decorative material is not adhered to the adhesive surface of the sheet, the aggregates are exposed by the washing, and a pattern or a washed surface can be formed. The laid sheet comes into surface contact with the formwork and has a large contact area, so that the occurrence of breakage or displacement due to the casting of the inorganic curable composition can be suppressed.
Therefore, it is not necessary to temporarily fix the form to the formwork by a temporary fixing means such as a double-sided adhesive tape, but the sheet may be temporarily fixed to the formwork by the temporary fixation means as necessary. In addition, joints (for example, polyurethane or the like) for preventing adhesion of a mortar composition or the like are provided in a gap (joint) between the arranged decorative materials and a gap (joint) between the mold and the decorative material. Joint bars made of flexible plastics).

Further, in the case of using a sheet on which a coating layer containing an adhesive or a curing retardation layer is formed, a kit in which decorative materials are previously arranged or arranged in the adhesive layer without disposing decorative materials in a mold frame. The sheet may be provided in the form. For example, a unit tile can be formed by sticking a plurality of tiles as decorative materials continuously or scattered in the surface direction on the surface of the adhesive coating layer. A plurality of tiles are often arranged adjacent to each other (continuously) in the plane direction (for example, the vertical direction, the horizontal direction, and the vertical and horizontal directions) or at intervals. By using such a decorative material kit sheet, there is no need to separately arrange decorative materials in the formwork, and only the decorative material kit sheet produced in a separate process needs to be disposed in the formwork. Efficiency can be increased. 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 can be used.
The decorative material may be flat, and the tile may be a mosaic tile or a split tile in addition to a normal tile. When manufacturing concrete products, if necessary,
A reinforcing material such as a reinforcing bar may be provided in the mold to cast the inorganic curable composition.

The decorative material kit film such as the unit tile is useful for producing a decorative finish concrete product such as a precast concrete plate. That is, the decorative material kit sheet is placed on a concrete casting formwork with the back surface of the decorative material such as the tiles facing upward, concrete is cast and cured, then the mold is removed, and the adhesive sheet is removed. By exposing the surface of the decorative material and washing the surface of the decorative material with water, the uncured inorganic curable composition (cement, etc.) that has wrapped around the surface of the decorative material is washed away, thereby integrating with the decorative material. Precast concrete boards can be manufactured. That is, even when the inorganic curable composition wraps around the surface of the decorative material such as tiles, the curing retardation component of the sheet or the curing retardation layer can suppress the curing of the inorganic curable composition, resulting in non-curing (semi-cured or uncured). ) State, the surface finish for removing the inorganic curable composition from the surface of the decorative material can be efficiently and perfectly performed by a simple operation such as washing with water.

The cement 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-hardened high-strength cement, burnt gypsum, etc.) Self-hardening cement; lime slag cement, blast furnace cement, etc .; 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),
It may be used as a mortar composition or a concrete composition containing fine aggregate such as sand, silica sand, and pearlite, and coarse aggregate. In addition, when the pattern is formed by using the above-described curing retardation sheet and aggregate exposed on the surface with washing, an aggregate, particularly a mortar composition including coarse aggregate is often used, and the decorativeness is reduced. In order to increase the surface, at least a part of the surface of the coarse aggregate is often smooth. The paste composition and the mortar composition are, if necessary, a coloring agent, a curing agent, a curing accelerator such as calcium chloride, a water reducing agent such as sodium naphthalene sulfonate, a coagulant, carboxymethyl cellulose, methyl cellulose, and polyvinyl alcohol. It may contain various additives such as a thickener, a foaming agent, a waterproofing agent such as a synthetic resin emulsion, and a plasticizer.

The curing retardation sheet of the present invention can be used to manufacture various concrete products, for example, concrete panels such as curtain walls and wall materials, concrete blocks, and the like.
In particular, it is useful for the production of decorative concrete products (for example, precast concrete plates).

[0051]

Since the curing retarder of the present invention is composed of a specific polyester, it has a high curing inhibiting ability with respect to cement despite its low solubility in water. Therefore, it is useful for suppressing outflow due to moisture and forming a pattern or a washout surface on the surface of a concrete product with high accuracy. The curing retardation sheet of the present invention has a curing retarder composed of the polyester, which is applied to the sheet, so that even when the mortar composition is cast, the flow of the curing retardant can be suppressed, and the mortar composition and Curing at the contact surface can be uniformly suppressed, and a pattern and a washout surface can be accurately formed on the surface of the concrete product. In addition, since the attached matter can be removed from the cosmetic material by washing, damage to the cosmetic material can be suppressed. Furthermore, a pattern and a washout surface can be simply and efficiently formed on the surface of a concrete product by a simple operation of laying a sheet in a mold or laying a sheet in a mold and placing a decorative material. In particular, even a complicated pattern can be easily formed on the surface of the concrete product, and the decorative property can be improved.

[0052]

EXAMPLES The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 and Comparative Example 1 In a 1-liter three-necked flask equipped with a stirrer and a thermometer, 204 g of ethylene glycol and oxalic acid 29 were added.
6 g (molar ratio = 1: 1) was added, the temperature was raised from room temperature to 150 ° C. over 3 hours with stirring, and then from 150 ° C. to 210 ° C. over 24 hours. The water generated during this reaction process is continuously removed from the system, and the temperature is reduced to 210 ° C.
When the reaction reached, the reaction was stopped to obtain an oily polyester. A polyester was obtained in the same manner as described above, except that a polyhydric alcohol and a polycarboxylic acid shown in Table 1 were used instead of the combination of ethylene glycol and oxalic acid. As a comparative example, a polyester was prepared in the same manner as above, except that pentanediol was used instead of ethylene glycol and phthalic acid was used instead of oxalic acid. In addition, the obtained polyester was oily, and the weight average molecular weight was all in the range of 2000 to 8000.

The performance of the obtained oily polyester as a curing retarder was examined by the following method. That is,
Portland cement / sand / water = 100/200/55
The mortar (weight ratio) of 600 g was placed in a polypropylene container having a diameter of 12 cm to flatten the surface. Then
A polypropylene ring (diameter: 5 cm, height: 3 cm, thickness: 0.3 mm) was pushed into the flattened mortar to a position where the height became half, and partially buried. After preparing the mortar, within 10 minutes, the oily polyester is poured into a ring so as to have a layer height of 2 to 3 mm and cast on the mortar surface, and the top of the polypropylene container is sealed with a food wrapping film. , Left for 1 hour. Next, the entire polypropylene container was transferred into an oven at 50 ° C. and left to cure for 8 hours. After curing, the polypropylene container was removed and left at room temperature for 55 hours to cure the mortar. The ring and the remaining oily polyester were removed from the cured mortar, and the contact surface between the oily polyester and the mortar was washed out with a toothbrush while washing with water and air-dried, and then the washability was visually evaluated according to the following criteria. In addition, a blank test for washing out in the same manner as described above without using the oily polyester was also performed. In the blank test, the surface of the cured mortar was dense and smooth, almost no sand particle shape was recognized, and the surface was cement-colored on average. Excellent: The effect of retarding the hardening is remarkable, and the depth of the mortar surface is 2
Good: The sand particles were clearly exposed, and a clear difference in roughness and hue was recognized between the inner region and the outer region of the ring. Good: Blank test or ring Although the difference in hue due to sand exposure is clearly compared to the outer area of
There is no big difference in surface smoothness and the degree of exposure of sand particles is small. No: No difference in appearance from the blank test.

[0054]

[Table 1] Example 2 In an autoclave having a capacity of 10 liters equipped with a stirring blade,
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
Organic peroxide (Nippon Oil & Fats Co., Ltd.)
Co., Ltd., “Perbutyl O”) was added at a concentration of 50 ppm and mixed with cobalt acetate as a crosslinking catalyst at a concentration of 50 ppm. Mix the mixture with a stainless steel vat (25cm × 40cm × 5c)
m) to a height of 2 cm, and in a furnace, 12
The composition was cured by heating at 0 ° C. for 15 minutes. The cured product was cooled to room temperature, coarsely pulverized by a crusher, and further pulverized by a freeze pulverizer to an average particle size of 200 μm or less to obtain a powdery cement setting retarder.

Next, the above-mentioned powdery cement setting retarder was evenly sprayed on the entire surface of the pressure-sensitive adhesive applied surface of a 5 cm-wide tape (Strong Adhesive Type for Corrugated Cardboard Packaging) coated with the pressure-sensitive adhesive. Excess powder was brushed off. The obtained tape is used for a wooden concrete plate form (with an internal capacity of 1
(m × 1 m × (depth) 10 cm) was attached at intervals of 10 cm with the powder adhesion side up. A mortar of Portland cement / sand / water = 100/200/55 (weight ratio) is poured into the mold so as to have a height of 3 cm.
After arranging rebars (diameter 1 cm × 80 cm) at intervals of cm, the mortar was further cast so as to have a total height of 6 cm. After being left at room temperature for 168 hours, the cured molding plate was released from the mold, the adhesive tape was removed, and then washed with a scrubbing brush while washing with water. as a result,
Only the contact area with the tape was washed out to a depth of 2 to 3 cm, and 5 cm wide washed-out surface having a natural color of sand and a rough surface due to sand particles was clearly formed at 10 cm intervals.

Example 3 10 parts by weight of 2-hydroxyethyl methacrylate and an organic peroxide (manufactured by NOF Corporation, at room temperature) were added to 100 parts by weight of an oily unsaturated polyester prepared in the same manner as in Example 2. A polymerizable composition was prepared by adding and mixing 3 parts by weight of cobalt acetate as a crosslinking catalyst at a concentration of 50 ppm. This polymerizable composition is applied to a 50 μm-thick polyethylene terephthalate sheet at an application amount of 50 g / m ² , and is cured by passing it through an oven at 150 ° C. for 30 seconds while heating. Obtained. The obtained sheet was slit to a width of 5 cm to obtain a long sheet.

An inner wall (1 m × 1 m inner wall) of a concrete formwork (30 cm × 1 m × (depth) 1 m) has an interval of 10 cm.
Then, the long sheet was stuck in a lattice shape with the application surface facing the inside of the mold, and the same mortar as in Example 2 was cast.
After curing for 8 hours, the cured mortar was released from the mold. When the surface of the hardened mortar was washed out in the same manner as in Example 2, the contact portion with the cement hardening delay sheet was washed out at a depth of about 2 mm, and a gobang-like pattern was clearly formed.

Example 4 A viscous oily unsaturated polyester (weight average molecular weight 1950) was prepared in the same manner as in Example 2 except that 3603 g (31.1 mol) of maleic anhydride and 2677 g (29.1 mol) of glycerin were used. I got 10 parts by weight of butyl acrylate was added to 100 parts by weight of the obtained unsaturated polyester, and an organic peroxide ("Perbutyl O" manufactured by NOF Corporation) was added to 100 parts by weight of the total amount of both. Parts by weight were added and mixed at 50 ° C. to prepare a solution of the polymerizable composition. The obtained polymerizable composition was dried with a basis weight of 3
A 0 g / m ² polyester nonwoven fabric was impregnated, excess composition was removed by squeezing with a roll, and the impregnated nonwoven fabric was heated in an oven at 150 ° C. for 30 seconds to obtain a cement setting retardation sheet. After the obtained curing retardation sheet was laid on the entire bottom surface of the wooden formwork used in Example 2, a square tile (10 cm × 10 cm ×
(Thickness: 8 cm) and joint bars (cross section: 10 mm × 10 mm square) were alternately arranged, and the mortar used in Example 2 was cast. After leaving to cure at room temperature for 168 hours, the concrete molded product was released from the mold and the tile surface was washed with water. The adhesion on the tile surface could be removed smoothly only by washing with water, using a wire brush, spatula, etc. No removal work was required.

Example 5 An oily unsaturated polyester (weight average molecular weight: 540) was obtained in the same manner as in Example 2, except that 3450 g (35.2 mol) of maleic anhydride and 2800 g (45.2 mol) of ethylene glycol were used. Was. The resulting unsaturated polyester was brush-coated on the bottom surface of the wooden formwork used in Example 2 at 10 cm intervals to a width of 10 cm. Example 2 in the mold
The mortar used in Example 2 was cast at a height of 5 cm, the reinforcing bars used in Example 2 were arranged at intervals of 20 cm, and the mortar was further cast so as to have a total height of 10 cm. After curing in the same manner as in Example 2, the concrete molded product was released from the mold and washed out, and sand and cement were washed out at a depth of about 2 mm only at the site where the oily unsaturated polyester was applied. 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. Further, the non-coated portion of the unsaturated polyester was cured, and the effect of the curing delay by the unsaturated polyester was not affected.

Example 6 An oil-saturated polyester (weight average molecular weight: 490) was obtained in the same manner as in Example 5, except that 4090 g (34.6 mol) of succinic acid and 2770 g (44.6 mol) of ethylene glycol were used. Using the obtained saturated polyester,
When the ability to retard cement setting was examined in the same manner as in Example 5, only the application site of the oily saturated polyester was washed out, and a relatively smooth washout surface having a natural color of sand was formed.

Example 7 Example 5 was repeated except that 3430 g (35.0 mol) of maleic anhydride and 2387 g (38.5 mol) of ethylene glycol were used, and after the reaction temperature reached 210 ° C., the reaction was further continued for 13 hours. The polymer was obtained by stopping the reaction at the time when stirring became impossible. Since this polymer was glassy at room temperature and was unnecessary as a solvent, its molecular weight could not be measured by gel permeation chromatography. The obtained polymer was pulverized by a crusher and a freeze pulverizer using liquid nitrogen to obtain a powder having an average particle diameter of 200 μm or less. Except for spraying the obtained powder on a tape coated with an adhesive,
When the curing retarding ability was examined in the same manner as in Example 2, only the contact portion with the tape was washed out to a depth of about 2 mm, and 5c
Washout surfaces of m width were clearly formed at 10 cm intervals.

Examples 8 to 10 and Comparative Example 2 Unsaturated polyesters were obtained in the same manner as in Example 2, except that the polycarboxylic acid component and the polyhydric alcohol component shown in Table 2 were used. Table 2 also shows the weight average molecular weight of the obtained unsaturated polyester.

[0063]

[Table 2] An organic peroxide (“Perbutyl O” manufactured by NOF Corporation) was used for 100 parts by weight of the obtained unsaturated polyester.
3 parts by weight, 50 ppm of cobalt acetate as a crosslinking catalyst
And a polymerizable composition was prepared by mixing. The polymerizable composition was applied to a 50 μm-thick polyethylene terephthalate sheet at an application amount of 50 g / m ² , and was passed through an oven at 150 ° C. for 30 seconds to be cured, thereby obtaining an application sheet. [Water immersion test] 5 cm x 10 cm of the obtained coated sheet
To prepare a sample. The obtained sample was immersed in pure water for 5 seconds, pulled up, allowed to stand on a filter paper with the unsaturated polyester coated side up, and the change of the sample was observed for 10 minutes. The following results were obtained. Obtained. Example 8: A strong curl occurred on the coated sheet, but the wrinkles were minute and the unsaturated polyester coating layer was not peeled off. Example 9: The coated sheet was curled, but the coated surface of the unsaturated polyester did not change, and no wrinkles or peeling was observed. Example 10: The coated sheet slightly curled, but no significant change was observed. Comparative Example 2: Almost no change was observed in the coated sheet.

[Wash-out test] Further, the applied sheet was
cm, and a long sheet was obtained. Wooden formwork (1m
X 1m x (depth) 10cm) on the bottom 10cm
Then, the long sheet is attached with the application side up, and the mortar used in Example 2 is cast so as to have a height of 3 cm.
After arranging rebars (diameter 1 cm x 80 cm) at intervals of 20 cm, the mortar was further cast so as to have a total height of 6 cm. After standing at room temperature for 168 hours, the cured molding plate was released from the mold, the long sheet was removed, and the work was performed with a scourer while washing with water. The following results were obtained.

Example 8: Depth 2 at contact portion with sample sheet
A recess of about mm was formed, and good washability was observed. Example 9: A concave portion having a depth of about 2 mm was formed at a contact portion with the sample sheet, and good washability was recognized. Example 10: A concave portion having a depth of about 1 mm was formed at a contact portion with a sample sheet, and washability was recognized.
9 and 9, the depth of the concave portion was smaller.

Comparative Example 2: Although a change in hue was observed at the contact portion with the sample sheet, no change was observed in the surface roughness as compared with the non-contact portion with the sample sheet.

Example 11 100 parts by weight of the unsaturated polyester (terephthalic acid content: 5% by weight) obtained in Example 8 was added to styrene 10
A polymerizable composition was prepared by adding and mixing 3 parts by weight of organic peroxide ("Perbutyl O", manufactured by NOF Corporation) and 50 ppm of cobalt acetate as a crosslinking catalyst at a concentration of 50 ppm. Except for using this polymerizable composition, a coated sheet holding a cured product of the unsaturated polyester was prepared in the same manner as in Example 8, and the same water immersion test and washing test as in Example 8 were performed. As a result, in the water immersion test, there was no noticeable curl on the sample sheet, and no change was observed on the unsaturated polyester coated surface. Also, in the washout test, the depth of about 2 mm at the contact area with the long sheet
Was formed.

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Claims (28)

[Claims] 1. A polycarboxylic acid component containing a polycarboxylic acid having a main chain of 2 to 6 carbon atoms or a derivative thereof,
4. A cement setting retarder composed of a polyester obtained by reaction with a polyol component containing a polyhydric alcohol or a condensate thereof according to 4. 2. The cement setting retarder according to claim 1, wherein the polycarboxylic acid is a saturated dicarboxylic acid having a main chain having 2 to 5 carbon atoms. 3. The cement set retarder according to claim 1, wherein the polycarboxylic acid has an ethylenically unsaturated bond and has a main chain of an unsaturated dicarboxylic acid having 4 to 6 carbon atoms. 4. The main repeating unit of the polyester is:
2. The composition according to claim 1, which is composed of a repeating unit having 4 to 9 carbon atoms.
The cement setting retarder according to the above. 5. The cement set retarder according to claim 1, wherein the polycarboxylic acid comprises maleic acid or maleic anhydride. 6. The cement setting retarder according to claim 1, wherein the polycarboxylic acid component further contains an aromatic dicarboxylic acid or a derivative thereof. 7. The cement retarder according to claim 6, wherein the content of the aromatic dicarboxylic acid is 0.1 to 30% by weight based on the whole polyester. 8. The cement setting retarder according to claim 6, wherein the aromatic dicarboxylic acid is at least one selected from phthalic acid, terephthalic acid, isophthalic acid and derivatives thereof. 9. The cement setting retarder according to claim 1, wherein the polycarboxylic acid component comprises maleic acid or maleic anhydride and an aromatic dicarboxylic acid or a derivative thereof. 10. The polyhydric alcohol is ethylene glycol, propylene glycol, trimethylene glycol,
2. The at least one member selected from the group consisting of tetramethylene glycol, dioxyethylene glycol, trioxyethylene glycol, polyoxyethylene glycol, dioxypropylene glycol, trioxypropylene glycol, polyoxypropylene glycol, and glycerin. The cement setting retarder according to the above. 11. A polyester having a weight average molecular weight of 30.
The cement set retarder according to claim 1, wherein the amount is from 0 to 100,000. 12. The polyester having a weight average molecular weight of 30.
The cement set retarder according to claim 1, wherein the amount is from 0 to 5000. 13. A reaction product of a dicarboxylic acid component containing at least maleic acid or a derivative thereof and a diol component containing an aliphatic diol having 2 to 4 carbon atoms or a condensate thereof, and having a molecular weight of 300 to 50,000. 2. The cement setting retarder according to claim 1, wherein the cement setting retarder comprises an unsaturated polyester. 14. The cement hardening retarder according to claim 1, which is composed of a cured product of an unsaturated polyester. 15. The cured product of a polymerizable composition containing an unsaturated polyester and a polymerization initiator.
The cement setting retarder according to the above. 16. The cement setting retarder according to claim 14, wherein the cured product is a cured product of a polymerizable composition containing an unsaturated polyester, a polymerizable vinyl monomer and a polymerization initiator. 17. The cement hardening retarder according to claim 16, wherein the polymerizable vinyl monomer is a polymerizable monomer selected from styrene-based monomers, acrylic-based monomers and methacrylic-based monomers. 18. The cement setting retarder according to claim 16, wherein the polymerizable composition contains the polymerizable monomer in an amount of 1 to 500 parts by weight based on 100 parts by weight of the unsaturated polyester. 19. A cured product of a polymerizable composition containing at least one polymerization accelerator selected from organic acid cobalt salts, β-diketones, aromatic tertiary amines, and mercaptos. The cement retarder according to claim 14. 20. The cement hardening retarder according to claim 19, wherein the concentration of the polymerization accelerator in the polymerizable composition is 10 to 1000 ppm. 21. The cement hardening retarder according to claim 14, wherein the hardened product is a granular material. 22. A reaction between a dicarboxylic acid component containing a saturated or unsaturated aliphatic dicarboxylic acid having a main chain of 2 to 6 carbon atoms or a derivative thereof, and a diol component containing a diol having 2 to 4 carbon atoms or a condensate thereof. And a main curing unit comprising a polyester whose main repeating unit is a repeating unit having 4 to 9 carbon atoms. 23. The polyester, wherein the main chain has 2 to 6 carbon atoms.
Dicarboxylic acid component containing saturated or unsaturated aliphatic dicarboxylic acid or a derivative thereof and at least one aromatic dicarboxylic acid or a derivative thereof selected from phthalic acid, terephthalic acid, and isophthalic acid, and a carbon number of 2 to 4 23. The cement hardening retarder according to claim 22, which is a polyester obtained by a reaction with a diol component containing the diol or a condensate thereof. 24. A polycarboxylic acid component having a main chain containing a polyvalent carboxylic acid having 2 to 6 carbon atoms or a derivative thereof;
A cement-setting retardation sheet, wherein a composition comprising a cement-setting retarder composed of a polyester obtained by reacting with a polyol component containing a polyhydric alcohol or a condensate thereof according to any one of (1) to (4), is held on a substrate sheet. 25. A composition comprising an unsaturated polyester,
25. The cement setting retardation sheet according to claim 24, which is obtained by applying or impregnating a nonporous sheet or a porous sheet, and curing by heating. 26. A composition comprising an unsaturated polyester,
The cement setting retardation sheet according to claim 25, comprising an unsaturated polyester and a polymerization initiator. 27. A composition comprising an unsaturated polyester,
The cement setting retardation sheet according to claim 25, comprising an unsaturated polyester, a polymerizable monomer, and a polymerization initiator. 28. A substrate sheet which is coated or impregnated with (1) a composition containing a powdery polyester and a pressure-sensitive adhesive or an adhesive, or (2) a pressure-sensitive adhesive layer or an adhesive layer of the substrate sheet. 25. The cement setting retardation sheet according to claim 24, which is obtained by adhering a powdery polyester.