JP3649527B2 - Molded product for delaying cement hardening and method for producing surface-decorated concrete product using the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a molded article for retarding cement hardening, a surface-decorated concrete useful for obtaining a surface-decorated concrete product such as a precast concrete board (hereinafter abbreviated as a PC board) in which the concrete surface is decorated with a decorative material such as a tile. The present invention relates to a kit for manufacturing a product, a manufacturing method thereof, and a manufacturing method of a surface-decorated concrete product.
[0002]
[Prior art]
A concrete product in which the surface of a PC board or the like is decorated with a decorative material such as a tile is widely used as a wall material in the civil engineering and building field. The PC board is usually manufactured as follows.
[0003]
(1) Apply an adhesive to the surface of a plastic sheet or film (for example, a sheet made by braiding a stretched yarn made of polypropylene), and then place a tile on the surface (front) surface It arrange | positions with a predetermined | prescribed arrangement | sequence so that it may contact | connect an adhesive, and it sticks and produces a unit tile.
(2) Arrange the unit tiles on the bottom surface of the mold so that the attached tiles are on the top surface.
(3) In order to prevent the concrete from flowing into the joints between the tiles, a pad made of plastics or foamed urethane foamed into a shape corresponding to the joints of the tiles is applied.
(4) Place concrete on it. Reinforcing bars are provided for reinforcement as needed.
(5) Apply curing and harden the concrete.
(6) The hardened concrete plate is removed from the mold, and the plastic sheet or film and the filling are removed, and the hardened concrete cement component (hereinafter referred to as “sloping”) is wound around the tile surface through the gap between the fillings. Cleaning and makeup work is performed.
[0004]
Of the above-described series of steps, padding is performed on the joints of the tiles in accordance with the design requirements of the external appearance of the PC board. A groove having a predetermined depth (hereinafter referred to as “joint groove”) is formed in the joints between the tiles. For example). However, if the filling method is incomplete, a large amount of concrete cement component flows into the gap between the tile and the filling material, and between the filling materials and hardens. Since it is difficult to completely remove the hardened “noro” and the commercial value of the PC board may be lost due to the remaining “noro”, the operation of applying the above-mentioned padding is extremely complicated and complicated. Work. In addition, the removal of “soil” after curing the PC plate and the makeup work involve manual work with a wire brush, spatula, sandpaper, etc., so that work efficiency is low and costs are increased.
[0005]
On the other hand, there is also a need for a PC board decorated with a plurality of decorative materials having a non-constant shape, which is formed of natural stone, crushed stone, glassware, pottery, ceramic plate, metal product, mortar or concrete product instead of tiles. . However, in such a PC board, there is often no suitable padding to be filled in the joint portion, and the surface shape of the decorative material is complicated, so that it takes an extremely long time to remove the “loose”. Therefore, it is very difficult to manufacture a PC board having the decorative material as described above.
[0006]
In JP-A-3-224953, in order to solve the above-mentioned problems in the joints, an aqueous mixed solution of sodium silicate and inorganic acid salt is injected into the joints between the decoration materials, and the PC board is completed and washed with water. The method of removing by is proposed. In addition, as a method of removing "slope", after applying concrete curing retarder to the inner surface of the mold in advance, or pasting paper, woven fabric, etc. impregnated with concrete curing retarder, disposing decoration materials, A method has been proposed in which concrete is placed, and after the concrete is hardened, the PC plate is removed from the mold and the uncured “soil” is removed by washing with water (Japanese Patent Laid-Open No. 54-119522, JP-A-54-14120 and JP-A-6-47725). Furthermore, Japanese Patent Laid-Open No. 48-1017 discloses a foam having a hole in accordance with the shape and arrangement of the decoration material in order to solve the problems associated with filling work of the filling into the joint portion and removal work of “slope”. After creating a molded product, applying a concrete retarder to it, placing it in the mold, placing a decorative material in each hole, placing the concrete, curing, demolding, and uncured cement There has been proposed a method of removing a part by washing with water.
[0007]
However, all of these methods involve complicated work and additional manual work such as applying a retarder on the inner surface of the mold or attaching a retarder impregnated woven fabric, etc. Therefore, it is difficult to increase workability and productivity of concrete products. Further, in the method described in Japanese Patent Laid-Open No. 48-1017, it is necessary to prepare a mold of a foam molded product for each decorative design of the PC board, so that the versatility is lacking and the cost is increased.
[0008]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a cement hardening delay-molding product, a surface-decorated concrete product manufacturing kit, and a method for manufacturing these that can easily and efficiently form a joint groove having a certain depth between decorative materials of the surface-decorated concrete product. It is to provide.
Another object of the present invention is to provide a cement-setting delayed molded product and a surface-decorated concrete product manufacturing kit, which can simplify the surface cosmetic work after the concrete is hardened, and can easily obtain a beautiful surface-decorated concrete product, and these It is to provide a manufacturing method.
Still another object of the present invention is to provide a highly versatile molded article for retarding cement hardening and a kit for producing a surface-decorated concrete product that can easily perform surface decoration of a concrete product regardless of the type and design of the decorative material. And providing a method for manufacturing these.
Still another object of the present invention is to provide a method for producing a surface-decorated concrete product that can easily and efficiently produce a highly decorative product and is excellent in versatility.
[0009]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventor is composed of a porous body that can be indented by pressing, and when a molded product having a cement hardening retarding ability is used, the surface of the molded product is used. It has been found that by pressing and arranging the decorative material, a joint groove having a predetermined depth can be easily and accurately formed, and hardening of the cement component flowing into the surface of the decorative material can be reliably suppressed. Completed the invention.
[0010]
  That is, this invention provides the molded article for cement hardening delay which was comprised with the porous body which can be indented by press, and was equipped with the cement hardening delay ability.The porous body has a tensile elongation at break of 0 to 80% and a tensile elastic modulus of 8000 to 300000 kgf / cm. ² Or a bulk density of 0.1 to 0.8 g / cm. ^Three A porous body (1) having a cement hardening retarding ability, or a porous body having a hardening retarding layer (2) having a cement hardening retarding ability formed on the surface of the porous body. The porous body (1) having the cement hardening retarding ability or the hardening retarding layer (2) is composed of a resin capable of developing the cement hardening retarding ability by hydrolysis or a resin having a phosphonic acid group, or Contains cement set retarder.
[0011]
  This molded product may be formed in a sheet shape, and in this case, it may have a base sheet layer on one side.Yes.
[0012]
  Also,PreviousThe porous body (1) having a cement hardening retarding ability or the hardening retarding layer (2) having a cement hardening retarding ability may be composed of a resin having a cement hardening retarding ability such as unsaturated polyester, and phosphoric acid. Or a salt hardening agent such as a salt thereof, boric acid or a salt thereof, hexafluorosilicate, phosphonic acid, oxycarboxylic acid, keto acid, polyhydric phenol, lignin sulfonic acid, or saccharide may be contained.
[0013]
  The present invention is also composed of a porous body having cement hardening retarding ability or a porous body having a hardening retarding layer having cement hardening retarding ability formed on the surface.For cement hardening delayA method for producing a molded article, wherein the tensile elongation at break is 0 to 80%And tensile elastic modulus 8000 to 300,000 kgf / cm ² Foam molding of resin compositionAnd forming the porous bodyA method for producing a molded article for delaying cement hardening including the step of:
[0014]
  PreviousTreeThe expansion ratio of the fat composition is, for example, about 1.5 to 80 times. Furthermore, this manufacturing method may include a step of foam-molding a composition containing an unsaturated polyester and curing the unsaturated polyester by heating.
[0015]
  The present invention is also composed of a porous body having cement hardening retarding ability or a porous body having a hardening retarding layer having cement hardening retarding ability formed on the surface.For cement hardening delayA method of manufacturing a molded article, which is made by making fibersBulk density 0.1-0.8 g / cm ^Three ofProvided is a method for producing a cement hardening delay-molded article including a step of forming a porous body composed of a nonwoven fabric.
[0016]
  The present invention further provides a surface of the cement hardening delay molding,By pressing the decorative material and making it indented or depressed,Decorative materialIs arrangedProvided kit for manufacturing surface decorative concrete products. The decorative material may be attached to a cement hardening delay molding with an adhesive or an adhesive.
[0017]
  The present invention further provides a surface of the molded article for retarding cement hardening.Dressed inPress the decoration material and intrude the molded productOr depressionLet the decorationsBy holding the decorative materialA method for producing a kit for producing a surface-decorated concrete product to be provided is provided.
[0018]
  The present invention also providesSaidCement hardening delay moldingThe above-mentioned cement hardening delay molded article in which the decoration material is disposed on the surface by pressing the decoration material into the indentation or depression and holding it.Surface-decorated concrete product in which the decorative material is placed in the mold so that the decorative material is positioned above, the inorganic curable composition is placed and cured, and then the mold and the cement hardening delay molding are removed. Provides a manufacturing method.
[0019]
In this specification, “tensile rupture elongation” and “tensile elastic modulus” mean the tensile rupture elongation and tensile elastic modulus in a non-foamed state, respectively. In addition, the “tensile elongation at break” and “tensile modulus” of a resin composition composed of a thermosetting resin are the tensile elongation at break and tensile elasticity when the resin composition is cured without foaming, respectively. Means rate. “Sheet” means a two-dimensional structure regardless of thickness, and is used to include a film. In addition, “pressure-sensitive adhesive or adhesive” may be collectively referred to as “pressure-sensitive adhesive”. “Derivatives of polyvalent carboxylic acids” are acid anhydrides of polyvalent carboxylic acids, lower alkyl esters of polyvalent carboxylic acids (for example, detachable Cs such as methyl esters and ethyl esters)._1-4It is used to mean including an alkyl ester. Further, unless otherwise specified, “cement” means an inorganic substance that exhibits curability when mixed with water, and is used to include pneumatic 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 are sometimes simply referred to as “inorganic curable composition”. “Concrete product” means a product obtained by curing an inorganic curable composition.
[0020]
DETAILED DESCRIPTION OF THE INVENTION
The molded article for retarding cement hardening of the present invention is composed of a porous body. The porous body only needs to be indented by pressing. Such a porous body includes a porous body in which the pressing portion is crushed and depressed by pressing, and a porous body that is indented with plastic deformation by pressing. As a porous body, any of the foam of a resin composition, and the non-foamed body comprised with the nonwoven fabric etc. may be sufficient.
[0021]
A wide range of resins that can be foam-molded can be used as the resin contained in the resin composition constituting the foam. Examples of the resin include cyclohexane such as styrene resin (polystyrene, etc.), vinyl chloride resin, polyurethane, phenol resin, urea resin, epoxy resin, olefin resin (eg, polyethylene, polypropylene, etc.), methacrylic resin, polyamide, polyoctenylene, and the like. Examples include alkene ring-opening polymers and polycaprolactone. Moreover, you may use resin (for example, the polyester resin which can express cement hardening retardance by hydrolysis, resin which has a phosphonic acid group, etc.) which has cement hardening retardance. These resins can be used alone or in combination. Preferred resins include styrene resins such as polystyrene, vinyl chloride resins, olefin resins, polyamides, polyoctenylene, polycaprolactone, polyester resins (particularly unsaturated polyester resins) and the like. In the case of using an organic retarder as a cement curing retarder, a resin having a low melting point, for example, a melting point of 150 ° C. or lower (for example, polyoctenylene, polycaprolactone, etc.) is used in order to suppress thermal decomposition of the retarder. It is preferable to add an additive having a function of reducing the melting point and melt viscosity, such as a plasticizer, a rosin derivative, and a wax, to the resin composition.
[0022]
The resin composition may contain an inorganic powder in order to increase brittleness and facilitate intrusion due to pressing. Examples of inorganic powder include, but are not limited to, oxides such as silica, alumina, zinc oxide, iron oxide, and titanium oxide; clays such as diatomaceous earth, kaolin, talc, bentonite, clay, stone powder, volcanic ash, and coal ash -Minerals; carbon black, graphite; metal powder such as iron powder and aluminum powder; alkaline earth metal salts such as calcium carbonate and barium sulfate; molybdenum disulfide and the like. The amount of the inorganic powder used is appropriately determined according to the type of the resin, and is usually about 3 to 200 parts by weight, preferably 8 to 150 parts by weight, more preferably 20 to 20 parts by weight with respect to 100 parts by weight of the resin. About 100 parts by weight.
[0023]
The resin composition may contain other additives such as plasticizers, waxes, stabilizers, antioxidants, ultraviolet absorbers, colorants, pressure-sensitive adhesives, adhesives, and the like as necessary. These additives can be used alone or in combination.
[0024]
The foam that can be indented by pressing is composed of a resin composition having a tensile elongation at break of about 0 to 80%. Among such foams, highly brittle resin compositions, for example, tensile elongation at break is about 0 to 30%, preferably about 0 to 20%, more preferably about 0 to 15%, and tensile elasticity. The rate is, for example, 10,000 kgf / cm²Above (10000-300000 kgf / cm²Degree), preferably 15000 kgf / cm²Above (15000-150000kgf / cm²Degree), more preferably 25000 kgf / cm²Above (25000-100,000 kgf / cm²When the decorative material used for surface decorative concrete products is pressed, the foamed resin in the pressed part easily collapses and is indented (decorated). A recess corresponding to the shape of the material is formed. Such a foam is particularly suitable for obtaining a surface-decorated concrete product in which the depth of the joint groove between the decorative materials is, for example, 1 mm or more (for example, about 1 to 20 mm), preferably 2 mm or more (for example, about 2 to 10 mm). Useful.
[0025]
Of the foam, a resin composition having a certain degree of ductility, such as a tensile elongation at break of about 20 to 80%, preferably about 30 to 80%, and a tensile modulus of 8000 kgf / cm.²Above (for example, 8000-20000 kgf / cm²Degree), preferably 8000 to 14000 kgf / cm²Degree (for example, 8000 to 10,000 kgf / cm²When the decorative material is pressed, the foamed resin in the pressing part is recessed (depressed) and the peripheral part of the pressing part is convex. Raise. Such a foam is useful for obtaining concrete products having concave curved joint grooves and concrete products having shallow joint grooves (for example, about 0.3 to 2 mm).
[0026]
The expansion ratio of the foam (true specific gravity of the resin composition constituting the foam / bulk specific gravity of the foam) is not particularly limited, but for example, 1.5 times or more (1 0.5 to 80 times), preferably 1.8 times or more (about 1.8 to 20 times), more preferably 2 times or more (about 2 to 10 times). The expansion ratio of the foam is often about 2 to 5 times, particularly about 2 to 2.5 times. If the expansion ratio is too small, a joint groove having a desired depth may not be formed. The bubbles in the foam may be either open cells or closed cells, but are preferably uniform.
[0027]
The fibers constituting the nonwoven fabric include a wide variety of fibers, such as natural fibers such as cotton, straw, and pulp; rayon, acetate, polyamide fibers (nylon), polyester fibers, polyvinyl alcohol fibers, and acrylic fibers. And artificial fibers (chemical fibers) such as polyolefin fibers. These fibers can be used alone or in combination.
[0028]
The nonwoven fabric may contain a binder and other additives as necessary. Examples of the binder include rubber binders such as natural rubber and synthetic rubber, vinyl acetate resins such as polyvinyl acetate and ethylene-vinyl acetate copolymer, acrylic resins, polyester resins, polyamide resins, and chlorides. Vinyl resins, urea resins, urethane resins, epoxy resins, water-soluble viscous substances (for example, synthetic water-soluble polymers such as polyvinyl alcohol, polyacrylic acid, polyacrylamide, carboxymethyl cellulose, hydroxyethyl cellulose; locust bean rubber, guar gum, And natural water-soluble polymers such as gum arabic, gum tragacanth, pectin, sodium alginate, and carrageenan). Content of binder is 0-2000 weight part (for example, 10-2000 weight part) with respect to 100 weight part of fibers which comprise a nonwoven fabric, for example, Preferably it is 0-1000 weight part (for example, 50-1000 weight part). More preferably, it is about 0 to 500 parts by weight (for example, 100 to 500 parts by weight). Examples of other additives to be included in the nonwoven fabric include granular materials such as the exemplified inorganic powder and organic powder. The bulk density of the nonwoven fabric may be in a range where the indentation operation by pressing is not impaired, for example, 0.1 to 0.8 g / cm.^Three, Preferably 0.12 to 0.6 g / cm^ThreeDegree.
[0029]
The shape of the cement hardening retarding molded product of the present invention is not particularly limited, and may be any of a sheet shape, a block shape, etc., but is often a sheet shape. The thickness of the sheet-like molded product can be appropriately selected in consideration of the depth of the joint groove between the decorative materials of the concrete product and the handleability. When the decorative material is a tile or the like, the thickness of the sheet-like molded product is, for example, 0.8 to 30 mm, preferably about 1 to 15 mm (for example, about 3 to 10 mm). When the porous body is a foam, the required minimum thickness varies depending on the expansion ratio. For example, when the depth of the dent formed by the indentation (depression) of the sheet-shaped molded product is 3 mm, the sheet-shaped molded product composed of a foam having a foaming ratio of 2 times has a foaming ratio of 6 mm or more. A double sheet-like molded product requires a thickness of 4.5 mm or more.
[0030]
The sheet-like molded product may have a base sheet layer on one surface. The polymer constituting the base sheet layer is not particularly limited, and examples thereof include olefin resins such as polyethylene and polypropylene; polyesters such as polyethylene terephthalate and polybutylene terephthalate (particularly polyalkylene terephthalate); ethylene-vinyl acetate copolymer, ethylene -Acrylic acid copolymer; Acrylic resin; Polystyrene; Polyvinyl chloride; Polyamide; Polycarbonate; Polyvinyl alcohol, ethylene-polyvinyl alcohol copolymer and the like. These polymers can be used alone or in combination of two or more. The base sheet layer may be made of paper, a polyester nonwoven fabric, various woven fabrics, a braided product of polypropylene stretched yarn, or the like. The base sheet layer may be a single layer or a plurality of layers may be laminated. Moreover, the sheet | seat (film) which comprises a base material sheet layer may be unstretched, and may be uniaxially or biaxially stretched.
[0031]
The thickness of the base sheet layer is, for example, about 10 to 200 μm, preferably about 15 to 150 μm, and more preferably about 20 to 100 μm.
[0032]
Since the molded article for retarding cement hardening of the present invention is composed of a porous body that can be depressed by pressing, the decorative material is pressed into the porous body to be depressed (depressed) and held, and an inorganic curable composition When an object is placed, a joint groove is formed at a portion corresponding to the non-indented portion of the molded product. Therefore, not only a complicated operation of filling the joint between the decorative materials is required, but also the joint groove having a desired depth can be easily and accurately formed by adjusting the pressure when pressing. Therefore, the process before placing the inorganic curable composition can be greatly simplified. Moreover, since it is not necessary to provide a hole for each decoration material, the versatility is high and the manufacturing cost can be reduced.
[0033]
The molded article for retarding cement hardening of the present invention has a cement retarding ability. Such a molded article includes (A) a molded article composed of a porous body (1) having a cement hardening retarding ability, and (B) a cure retarding layer having a cement hardening retarding ability on the surface of the porous body ( 2) is formed.
[0034]
[Cement hardening delayed molding (A)]
In the molded article (A) composed of the porous body (1) having a cement hardening retarding ability, the cement hardening retarding ability is obtained by constructing the porous body with a resin having a cement hardening retarding ability, or the porous body. It can be imparted by adding a cement setting retarder to
[0035]
Molded products (A1) made of a porous material composed of a resin having a cement hardening retardancy include foam molded products (A11) composed of a resin having a cement cure retarding ability, and a resin having a cement cure retarding ability. Constructed non-woven fabric (A12) and the like are included. Molded articles (A2) composed of a porous body containing a cement hardening retardant include foamed molded articles (A21) containing a cement hardening retardant, non-woven fabric (A22) containing a cement hardening retardant, and the like. .
[0036]
The resin having a cement hardening retarding ability is not particularly limited as long as it is a resin having a retarding or inhibiting action on the hardening of cement, for example, a resin capable of developing a cement hardening retarding ability by hydrolysis (for example, polyester), Examples thereof include a resin having a phosphonic acid group. These resins may be used alone or in combination. Of these resins, polyester is preferred. The polyester can be obtained by a condensation reaction of a carboxylic acid component containing a polyvalent carboxylic acid or a derivative thereof and a polyol component containing a polyhydric alcohol or a condensate thereof.
[0037]
Examples of the polyvalent carboxylic 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, and adipic acid; maleic acid, maleic anhydride, fumaric acid, itacone Examples thereof include unsaturated polycarboxylic acids having 4 to 6 carbon atoms in the main chain such as acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid. The saturated carboxylic acid and unsaturated carboxylic acid may be used in combination. These polyvalent carboxylic acids can be used alone or in combination of two or more.
[0038]
In addition to the polyvalent carboxylic acid, the polyvalent carboxylic acid component may be an aliphatic polyvalent carboxylic acid (eg, azelaic acid, sebacic acid, etc.), an aromatic polyvalent carboxylic 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 selected from phthalic acid, terephthalic acid, isophthalic acid or derivatives thereof or a derivative thereof is used, the strength, elongation, flexibility, flexibility, Useful for adjusting properties such as water resistance.
[0039]
The content of the aromatic polycarboxylic acid with respect to the whole polyester is, for example, 0.1 to 30% by weight, preferably 0.1 to 20% by weight (eg 1 to 15% by weight), and more preferably 0.1 to 10%. It is about weight% (for example, 2-10 weight%).
[0040]
Preferred polyvalent carboxylic acid components include: (1) a polyvalent carboxylic acid component containing an unsaturated aliphatic dicarboxylic acid having 4 to 6 carbon atoms in the main chain or a derivative thereof (particularly at least maleic acid, maleic anhydride, fumaric acid). A polyvalent carboxylic acid component containing an 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 phthalic acid, terephthalic acid, and isophthalic acid. And a polyvalent carboxylic acid component containing at least one aromatic dicarboxylic acid or a derivative thereof.
[0041]
Examples of the polyol component include polyhydric alcohols having 2 to 4 carbon atoms, such as diols (for example, C such as ethylene glycol, propylene glycol, 1,3-butanediol, and tetramethylene glycol)._2-4Alkylene glycol), C_2-4Polyoxyalkylene glycols, which are condensates of alkylene glycols, such as dioxyethylene glycol, trioxyethylene glycol, polyoxyethylene glycol (hereinafter, these may be collectively referred to as polyethylene glycol unless otherwise specified), Dioxypropylene glycol, trioxypropylene glycol, polyoxypropylene glycol (hereinafter, these may be simply referred to as polypropylene glycol unless otherwise specified), polyoxytetramethylene glycol, etc .; polyols (for example, glycerin, diglycerin) , Polyglycerin and the like). These polyol components may be used alone or in combination.
[0042]
Preferred polyhydric alcohols include ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, dioxyethylene glycol, trioxyethylene glycol, polyoxyethylene glycol, dioxypropylene glycol, trioxypropylene glycol, polyoxypropylene Glycol and glycerin are included. In many cases, the polyhydric alcohol includes a polyhydric alcohol component composed of an aliphatic polyhydric alcohol having 2 to 4 carbon atoms (particularly a diol) or a condensate thereof.
[0043]
The molecular weight of the polyoxyalkylene glycol is, for example, a weight average molecular weight of 100 to 7500, preferably about 200 to 5000 (for example, 200 to 2500). When polyethylene glycol is used, the weight average molecular weight is often 300 or less. .
[0044]
The polyhydric alcohol may be used in combination with other polyols, for example, trimethylolethane, trimethylolpropane, pentaerythritol and the like as necessary. Of these polyesters, unsaturated polyesters, particularly unsaturated polyesters containing maleic acid or maleic anhydride as the polyvalent carboxylic acid component are preferred.
[0045]
The molecular weight of the polyester is not particularly limited, and can be selected from the range of, for example, a weight average molecular weight of 300 to 100,000 (for example, 300 to 25,000), preferably 300 to 50,000 (for example, 500 to 15000), and more preferably about 500 to 20,000. . The molecular weight of the unsaturated polyester is 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 about 500 to 2,500. There are many cases. The molecular weight is a weight average molecular weight in terms of polystyrene as determined by gel permeation chromatography.
[0046]
Polyesters such as unsaturated polyesters can be obtained by a conventional method, for example, by condensing a polyvalent carboxylic acid component and a polyhydric alcohol component in the presence of a catalyst. When an unsaturated polyvalent carboxylic acid such as maleic acid or maleic anhydride is used, the condensation reaction is often performed in the presence of a radical polymerization inhibitor such as hydroquinone. Polyester can be selected from the range of about 0.5 to 3 equivalents, preferably about 0.7 to 2 equivalents of polyhydric alcohol with respect to 1 equivalent of polycarboxylic acid. A polyester having a low molecular weight is often obtained by using either one of a polyvalent carboxylic acid and a polyol in excess.
[0047]
The resin having cement hardening retarding ability may be 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. As the polymerization initiator, various organic peroxides such as methyl ethyl ketone peroxide, cumene hydroperoxide, benzoyl peroxide, t-butylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, dicumyl Peroxides can be used. The amount of the polymerization initiator used is within a range that does not impair the polymerizability, for example, 0.5 to 5 parts by weight, preferably about 1 to 4 parts by weight, and 2 to 3 parts by weight with respect to 100 parts by weight of the unsaturated polyester. In many cases.
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, for example, styrene monomers such as styrene, α-methylstyrene, vinyltoluene, and alkyl groups such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate. Alkyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acrylic acid having about 20 to 20 (particularly 1 to 10 carbon atoms) , Monomers having functional groups such as glycidyl (meth) acrylate (hydroxyl group, carboxyl group, glycidyl group, etc.), esters of (meth) acrylic acid and polyhydric alcohols (polyethylene glycol, etc.) (for example, ethylene glycol mono ( Or di (Meth) acrylate, diethylene glycol mono (or di) (meth) acrylate, polyethylene glycol mono (or di) (meth) acrylate), and the like. As the vinyl monomer, vinyl esters such as vinyl acetate, halogen-containing vinyl monomers such as vinyl chloride, vinyl cyanides such as acrylonitrile, and olefin monomers such as ethylene and propylene can be used. These polymerizable monomers can be used alone or in combination of two or more.
Preferred polymerizable vinyl monomers include acrylic monomers and methacrylic monomers, particularly (meth) acrylic acid glycol esters.
[0048]
The amount of the polymerizable vinyl monomer used is in a range that does not impair the retarding ability and the handling property of the unsaturated polyester depending on the molecular weight of the unsaturated polyester, for example, 1 to 500 weights with respect to 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), or about 5 to 30 parts by weight.
The cured product of the unsaturated polyester is a component that constitutes the polymerizable composition (that is, the unsaturated polyester that constitutes the polymerizable composition (i), the polymerization initiator, and the component that constitutes the polymerizable composition (ii)). In addition to a saturated polyester, a polymerizable vinyl monomer, and a polymerization initiator, it may be a cured product of the polymerizable composition (iii) containing a polymerization accelerator. Examples of the polymerization accelerator include organic acid cobalt salts such as cobalt naphthenate and cobalt octylate, β-diketones or β-ketoesters such as acetylacetone and ethyl acetoacetate, aromatic tertiary amines, and mercaptos. 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 can be selected, for example, from a range of about 10 to 1000 ppm, preferably about 10 to 500 ppm (for example, 10 to 100 ppm), and may be about 30 to 50 ppm.
[0049]
Unsaturated polyester can be cured (crosslinked) at room temperature, but it is advantageous to cure at a temperature of about 60 to 200 ° C. in order to cure in a short time (for example, about 0.5 to 50 minutes). .
[0050]
The cement curing retarder may be a curing retarder or a setting retarder that reduces the curing rate of the cement, and an inorganic or organic cure retarder can be used. Inorganic cure retarders include phosphoric acid, boric acid or salts thereof, hexafluorosilicate, and the like. Organic curing retarders include phosphonic acids, oxycarboxylic acids, polyvalent carboxylic acids, keto acids, aromatic polyhydric alcohols, saccharides, humic acids, lignin sulfonic acids, monomers having a carboxyl group alone or copolymers or Such salts are included.
[0051]
Examples of phosphonic acids include aminodi (methylenephosphonic acid), aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), hexamethylenediamine Tetra (methylenephosphonic acid) or a salt thereof (for example, ammonium salt; alkali metal salt such as sodium or potassium; alkaline earth metal salt such as calcium, magnesium, or barium).
[0052]
Examples of oxycarboxylic acids include glycolic acid, lactic acid, malic acid, tartaric acid, citric acid, gluconic acid, gallic acid, oxycarboxylic acid such as 2,4,6-trihydroxybenzoic acid or salts thereof, ascorbic acid, isoascorbine Examples include lactones corresponding to oxycarboxylic acids such as acids. Examples of the polyvalent carboxylic acids include saturated polyvalent carboxylic acids such as oxalic acid, malonic acid, and succinic acid; unsaturated polyvalent carboxylic acids such as fumaric acid, itaconic acid, and maleic acid. Examples of keto acids include keto acids such as pyruvic acid and α-ketoglutaric acid or 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 or lignosulfonate (for example, calcium lignosulfonate). Monomers having a carboxyl group or copolymers or salts thereof include polymaleic acid, polyfumaric acid, styrene-maleic acid copolymer, polyacrylic acid, polymethacrylic acid, styrene- (meth) acrylic acid copolymer, Examples thereof include polymers such as (meth) acrylic acid ester- (meth) acrylic acid copolymers and ethylenesulfonic acid-acrylic acid copolymers or salts thereof (preferably, low molecular weight polymers or salts thereof). Among these curing retardants, inorganic curing retardants, 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.
[0053]
In this way, in the molded product (A) composed of the porous body (1) imparted with the cement hardening retarding ability, the hardening of the concrete is suppressed by the hardening retarding component that exudes from the porous body. The inorganic curable composition in a state can be easily washed away with water. In particular, unlike other curing retarders, the polyester hardly dissolves in water and hardly flows with bleed water from concrete. However, due to the strong alkalinity of concrete, the ester bond of polyester is hydrolyzed, and carboxyl groups and hydroxyl groups useful for retarding the curing are released. This hydrolysis rate increases as moisture in the concrete is used to harden the cement, and is maximized by the heat generation of the concrete during curing, and the liberated carboxyl group and hydroxyl group synergistically exhibit a large setting retarding ability. Let On the other hand, the concrete at the stage where the retarding ability is exhibited does not already have fluidity, and even if the retarding component is released by hydrolysis of the polyester, it does not dissolve and move in the bleed water. Therefore, curing retardance can be expressed only at a desired site, and a beautiful surface decoration can be accurately formed by washing after the cement is cured.
[0054]
[Manufacture of cement hardening delayed molding (A)]
The molded article (A) composed of the porous body (1) having a cement hardening retarding ability can be produced, for example, by the following method.
[0055]
For example, the foam-molded article (A11) composed of the resin having the ability to retard cement hardening includes the resin having the ability to retard cement hardening and, if necessary, additives such as other resins and inorganic powders. It can be produced by subjecting a resin composition having a tensile elongation at break of 0 to 80% to a conventional foam molding method. The foam molded article (A21) containing a cement hardening retardant includes, for example, the cement hardening retardant, the foam moldable resin, and additives such as inorganic powder as necessary, and tensile elongation at break. It can be produced by subjecting a resin composition having a degree of 0 to 80% to a conventional foam molding method.
[0056]
The preferred tensile elongation at break and tensile modulus of the resin composition to be subjected to foam molding are the same as the values described in the explanation of the foam. The tensile elongation at break and the tensile modulus can be adjusted by the type and degree of polymerization of the resin contained in the resin composition, the amount of the inorganic powder added, and the like.
[0057]
For example, in a resin composition having a tensile elongation at break of 0 to 80%, the inorganic powder is contained in an amount of about 3 to 200 parts by weight with respect to 100 parts by weight of the resin in the composition containing the foamable resin. Can be prepared. By adjusting the amount of the inorganic powder to, for example, about 5 to 200 parts by weight (preferably 8 to 150 parts by weight, more preferably 20 to 100 parts by weight) with respect to 100 parts by weight of the resin, When the decorative material is pressed, it is possible to obtain a foam in which the pressing portion easily collapses and intrudes with the pressing. Further, when the amount of the inorganic powder is adjusted to, for example, about 3 to 20 parts by weight (preferably 3 to 8 parts by weight) with respect to 100 parts by weight of the resin, plastic deformation is caused when the decorative material is pressed. Thus, it is possible to obtain a foam in which the pressing portion is recessed in a concave shape. When the foam-moldable resin is a cycloalkene ring-opening polymer such as polyoctenylene or the unsaturated polyester, the amount of the inorganic powder is about 3 to 100 parts by weight with respect to 100 parts by weight of the resin. In particular, in many cases, the amount is about 10 to 60 parts by weight. When the resin is a styrene resin or the like, the amount of the inorganic powder is about 3 to 100 parts by weight, particularly 5 It is often about 50 parts by weight.
[0058]
In the production of the foam molded article (A11), the amount of the resin having a cement hardening retarding capacity is, for example, 10 to 100% by weight, preferably 30 to 100% by weight, based on the entire resin composition to be subjected to foam molding. More preferably, it is about 40 to 100% by weight. In the production of the foam molded product (A21), the amount of the cement curing retarder used is, for example, 5 to 1000 parts by weight, preferably 10 to 700 parts by weight, more preferably 100 parts by weight of the foam moldable resin. Is about 20 to 300 parts by weight, and in particular often 30 to 150 parts by weight.
[0059]
As the foaming method, a method of curing a foam diaphragm formed by mechanical stirring with a curing agent, a method of using a generated gas released when a liquid raw material is resinized, a method of using a foaming agent, Although any method such as a method of removing soluble substances may be used, in many cases, a thermally decomposable chemical foaming agent is used and foamed by heating with (or after) molding. The expansion ratio is as described above.
[0060]
More specifically, when the resin constituting the resin composition to be subjected to foam molding is a thermoplastic resin, for example, addition of resin powder or pellets, a foaming agent, and inorganic powder as necessary A foam-molded article can be obtained by subjecting the mixture containing the agent to foaming by heating or the like and extrusion or injection molding. In addition, when the resin constituting the resin composition to be subjected to foam molding is a thermosetting resin (for example, unsaturated polyester), for example, a prepolymer, a foaming agent, and a curing agent, an inorganic powder, if necessary, etc. Transfer molding of the mixture containing the additive, or foam molding by casting the mixture onto a support (film, belt, drum, etc.) and heat treatment (casting method), etc. Alternatively, the foamed product can be obtained by curing the resin by heating after foam molding.
[0061]
In addition, the nonwoven fabric (A12) composed of the resin having a cement hardening retarding ability is, for example, a fiber composed of a resin having a cement hardening retarding ability, or a fiber coated with a resin having a cement hardening retarding ability, and If necessary, the mixture containing additives such as the binder can be produced by a conventional paper making method to form a porous body composed of a nonwoven fabric having a desired thickness. The nonwoven fabric (A12) can also be produced by paper-making a mixture containing fibers, a resin granule having cement hardening retarding ability, and, if necessary, additives such as the binder.
[0062]
The non-woven fabric (A22) containing the cement hardening retardant, for example, a conventional paper making method using a mixture containing a fiber coated with a composition containing a cement hardening retardant and, if necessary, an additive such as the binder. Can be manufactured by forming a porous body made of non-woven fabric. Moreover, the said nonwoven fabric (A22) can be manufactured also by making the mixture containing an additive, such as a fiber, the granule of a cement hardening retarder, and the said binder as needed.
[0063]
Papermaking can be performed by either dry or wet methods. The above-mentioned examples can be used as the fiber for papermaking. The fiber diameter of a fiber is 0.01-2000 micrometers, for example, Preferably it is 0.05-1000 micrometers, More preferably, it is about 0.1-200 micrometers. Moreover, the fiber length of a fiber is 0.1-10 mm, for example, Preferably it is about 0.5-5 mm. The fiber content in the nonwoven fabric (A12) or (A22) is, for example, about 60 to 99.5% by weight, preferably about 70 to 99% by weight. In fibers coated with a resin having a cement hardening retarding ability or a cement hardening retarder, the amount of the resin or the hardening retarder applied can be appropriately set within a range that does not impair the retarding action on cement hardening.
[0064]
In addition, a sheet-like molded product having a base sheet layer on one surface is obtained by attaching a base sheet to a conventional porous material molded by a conventional molding method (for example, extrusion molding, paper making, etc.). It can form by joining with an agent or an adhesive agent. In the case where the porous body is made of a thermoplastic resin, the mixture containing the thermoplastic resin powder is extruded and laminated on a base sheet, and is made of a thermosetting resin. For example, a sheet-like molded article having a base sheet layer can be obtained by applying the mixture containing a prepolymer or the like onto a base sheet and curing the mixture. The coating liquid for applying the mixture containing the prepolymer or the like to the base sheet may contain an organic solvent. Organic solvents include alcohols such as methanol, ethanol and isopropanol; aliphatic hydrocarbons such as hexane and octane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons Ketones such as acetone and methyl ethyl ketone; ethers; esters such as ethyl acetate; and mixed solvents thereof. In application, a brush roller, rubber spatula, etc. may be used, but industrially, application means used for normal coating, such as a dip coater, roll coater, gravure coater, air knife coater, reverse roll coater, Comma coaters, bar coaters, curtain coaters, sprays, etc. are often used.
[0065]
[Cement hardening delayed molding (B)]
In the molded article (B) in which the hardening retardation layer (2) having cement hardening retardation is formed on the surface of the porous body, the cement hardening retardation is a resin having cement hardening retardation. Or by adding a cement curing retarder to the curing retardation layer (2).
[0066]
In the molded product (B1) in which a curing retardation layer composed of a resin having a cement curing retardation ability is formed on the surface of the porous body, the molded product (B11) in which the porous body is composed of a foam of a resin composition. ), And a molded article (B12) in which the porous body is composed of a nonwoven fabric. In addition, the molded product (B2) in which a curing retarding layer containing a cement curing retarder is formed on the surface of the porous body is a molded product (B21) in which the porous body is composed of a foamed resin composition, The molded product (B22) etc. in which the material is composed of non-woven fabric are included.
[0067]
As the resin having cement hardening retarding ability and the cement hardening retarding agent, those exemplified in the section of the molded article for retarding cement hardening (A) can be used.
[0068]
The resin having cement hardening retardancy and the cement hardening retarder may be used alone or in combination to form the cure retarding layer (2). When the cement hardening retarder or the like is non-film-forming May be used in combination with a binder resin to form the curing retardation layer (2).
[0069]
Examples of the binder resin include chlorine such as polyvinyl acetate, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, acrylic resin, vinyl chloride-vinyl acetate copolymer, and chlorinated polypropylene. Examples thereof include cellulose-based resins such as modified polyolefin, acetylcellulose, acetylbutylcellulose, ethylcellulose, and nitrocellulose. These binder resins can be used alone or in combination of two or more.
[0070]
The amount of the binder resin used can be selected according to the type of the resin having cement hardening retardancy and the cement hardening retarder. When using a resin having a cement hardening retarding ability, a binder resin is not necessarily required. For example, 0 to 200 parts by weight of a binder resin, preferably 0 to 100 parts by weight with respect to 100 parts by weight of a resin having a cement hardening retarding ability. It can be selected from a range of about parts. Moreover, when using a cement hardening retarder, a hardening retarder is 5-1000 weight part with respect to 100 weight part of binder resin, Preferably it is 10-700 weight part, More preferably, it is about 25-500 weight part. .
[0071]
[Manufacture of molded product for delayed cement hardening (B)]
The cement hardening delay molding (B) can be produced, for example, by the following method. For example, a molded article in which a curing retarding layer composed of a resin having a cement curing retarding ability or a curing retarding layer containing a cement curing retarding agent is formed on the surface of a porous body composed of a foam of a resin composition (B11) (B21) includes the foamable resin and, if necessary, an additive such as the inorganic powder, and a conventional foamed resin composition having a tensile elongation at break of 0 to 80%. After forming into a desired shape by being subjected to a molding method, a coating liquid containing the resin having a cement hardening retarding ability or a cement hardening retarding agent, and if necessary, a binder resin, an inorganic powder, and other additives, It can be produced by applying to the surface of the molded foam or impregnating the foam and drying or curing.
[0072]
The preferred tensile elongation at break and tensile modulus of the resin composition to be subjected to foam molding are the same as the values described in the explanation of the foam. The tensile elongation at break and the tensile modulus can be adjusted by the type and degree of polymerization of the resin contained in the resin composition, the amount of the inorganic powder added, and the like. For example, a resin composition having a tensile elongation at break of 0 to 80% can be prepared in the same manner as in the production of the cement hardening retarded molded article (A). In addition, as the foaming method, the method described in the section for producing the cement hardening delay molding (A) can be used.
[0073]
The coating solution may contain, for example, the exemplified organic solvent. In the application, the above application means can be used. The thickness of the curing retardation layer (2) may be a thickness that exhibits a retardation effect on the curing of the cement, for example, 1 to 300 μm (for example, 5 to 200 μm), preferably 2 to 150 μm (for example, 5 to 120 μm), More preferably, it is about 5-100 micrometers (for example, 10-100 micrometers), and it is about 5-70 micrometers in many cases.
[0074]
Further, a molded article (B12) (B22) in which a curing retardation layer composed of a resin having cement curing retardation or a curing retardation layer containing a cement curing retardation agent is formed on the surface of a porous body composed of a nonwoven fabric. ), After making a mixture containing the fibers and, if necessary, additives such as the binder by a conventional paper making method to form a porous body composed of a nonwoven fabric having a desired thickness, Apply the coating solution containing the resin having cement hardening retarding ability or cement hardening retarding agent and, if necessary, binder resin, inorganic powder and other additives to the surface of the molded nonwoven fabric, or impregnating the nonwoven fabric. And dried or cured. The above-mentioned methods can be used as the paper making method and the method of forming the curing retardation layer.
[0075]
In addition, the sheet-like molded article which has a base material sheet layer in one surface can be obtained by the same method as the case of the said cement hardening delaying molded article (A).
[0076]
In the cement hardening delay molding (B), since the hardening of the concrete is suppressed by the hardening retarding component exuded from the hardening delay layer (2), the non-hardened inorganic curable composition (cement etc.) can be easily removed with water. Can be washed away.
[0077]
Since the molded product for retarding cement hardening of the present invention is a molded product which itself has a cement curing retarding ability as described above, a cement curing retarder is applied to the mold or the cement curing retarder is applied to the mold. There is no need for a troublesome work of attaching a woven fabric impregnated with sapphire.
[0078]
The molded article for delaying cement hardening of the present invention is useful in producing a surface-decorated concrete product that is integrally fixed with a decorative material. That is, the cement hardening delay molding is disposed in the mold, and is arranged so that the front surfaces of a plurality of decorative materials such as stones and tiles are in contact with the surface of the molding. In addition, when the hardening delay layer (2) is formed in the surface of the said molded article, a molded article is arrange | positioned so that the hardening delay layer (2) may be located upwards. The decorative material is pressed from the back and press-fitted to a predetermined depth. The decoration material may be pressed individually or a plurality of decoration materials may be simultaneously pressed. At this time, the pressing portion of the molded product is recessed (indented), and an indented portion (dented portion) corresponding to the shape of the decorative material is formed. The depth of the indented portion substantially corresponds to the depth of the joint groove between the decorative materials. Therefore, a joint groove having a desired depth can be easily and accurately formed by adjusting the pressure when pressing the decorative material. In addition, since the above-mentioned molded product for delaying cement hardening inhibits the hardening of cement at the joint, the depth of the joint groove is the sum of the depth of the indented portion and the cure delay depth at the joint (the depth at which the hardening retarding action is exerted). It corresponds to. When the indented portion is formed by plastic deformation of the porous body, the molded product may be heated to facilitate plastic deformation when the decorative material is pressed.
[0079]
As decoration materials, various materials, for example, natural stones such as cobblestone, black stone and iron flat stone, stone materials such as artificial stones, ceramic materials such as tiles, metal materials, glass materials, mortar or concrete materials, wood, woven fabrics, etc. Can be used. The decoration material may be flat, and the tile may be a mosaic tile or a split tile in addition to a normal tile. Moreover, when manufacturing a concrete product, you may arrange | position reinforcement materials, such as a reinforcing bar, in a formwork as needed, and may cast an inorganic curable composition.
[0080]
Next, an inorganic curable composition (a curable composition containing cement) is placed in a mold and cured by a conventional curing method such as curing. At that time, the molded product can uniformly suppress curing at the contact surface with the inorganic curable composition, so that the hardened concrete is removed from the mold and the molded product is removed, and the surface side of the decorative material ( The surface-decorated concrete product integrated with the decorative material can be easily removed by cleaning the contact surface side with the molded product with water, pressurized water, jet flow, etc., and removing the uncured composition adhering to the decorative material and joint groove. (Precast concrete board etc.) can be obtained.
[0081]
In addition, when using the molded product for delaying cement hardening, a kit for producing a surface-decorated concrete product in which a decorative material is arranged or arranged in advance on the molded product without placing a decorative material in the mold is placed in the mold. It may be arranged. For example, a plurality of decorative materials (for example, tiles, etc.) are arranged continuously or scattered in the surface direction on the surface of the cement hardening delay molding, and pressure is applied from the back surface of the decorative material in the same manner as described above. A kit for producing a surface-decorated concrete product such as a unit tile can be formed by placing the decorative material by indenting (depressing) the molded product. In addition, when the hardening delay layer (2) is formed in the surface of the said molded article, a decorating material is arrange | positioned on the surface of a hardening delay layer (2). In many cases, a plurality of decorative materials are arranged adjacent to each other (continuously) or spaced apart from each other in a surface direction (for example, a vertical direction, a horizontal direction, and a vertical and horizontal direction).
[0082]
In addition, the decoration material may be stuck to the said molded article with the adhesive or the adhesive agent. For example, the decorative material can be attached to the molded product by applying an adhesive or an adhesive to the molded product or the decorative material. This method is useful for a molded article made of a porous body that is depressed by plastic deformation and can hold a decorative material. As the pressure-sensitive adhesive or adhesive, for example, those exemplified as the binder can be used. The pressure-sensitive adhesive may be used in combination with a tackifier (for example, a petroleum resin, a terpene resin, a hydrocarbon resin such as a dicyclopentadiene resin, or a rosin derivative). In order to efficiently clean the surface of the decorative material in the decorative work of the surface-decorated concrete product integrated with the decorative material, the pressure-sensitive adhesive or adhesive has an adhesive strength or adhesive that can temporarily fix the decorative material. In the case where a material capable of imparting force or a decorative material is firmly bonded, a material that can be removed by washing is preferable. Moreover, you may stick a decoration material to a molded article with a double-sided adhesive tape. Such a kit can reliably prevent the decoration material from being detached.
[0083]
According to the kit for producing surface-decorated concrete products, it is not necessary to separately arrange the decoration material in the mold, and it is only necessary to arrange the kit produced in a separate process in the mold, thereby improving the work efficiency. be able to.
[0084]
The kit for producing a surface-decorated concrete product such as a unit tile is useful for producing a decorative concrete product such as a precast concrete board. That is, the kit is placed on a concrete casting form with the back surface of the decorative material such as the tile, the inorganic curable composition is placed and cured, and then demolded to delay cement hardening. The decorative material surface is exposed by removing the molded product, the surface of the decorative material is washed with water, and the non-curable inorganic curable composition (such as cement) that wraps around the decorative material surface is washed away. Can produce surface-decorated concrete products integrated with That is, even if the inorganic curable composition wraps around the surface of a decorative material such as a tile, the curing of the molded article can suppress the curing of the inorganic curable composition, and the non-cured (semi-cured or uncured) state Therefore, 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.
[0085]
Cement includes, for example, air-hardening cement (gypsum, lime such as slaked lime and dolomite plaster); hydraulic cement (eg, Portland cement, early strength Portland cement, alumina cement, rapid hardening high strength cement, baked gypsum etc.) Cement; lime slag cement, blast furnace cement, etc .; mixed cement). Preferred cements include, for example, gypsum, dolomite plaster and hydraulic cement.
[0086]
The cement may be used as a paste composition with water (cement paste), fine aggregates such as sand, silica sand, perlite, etc., or as a mortar composition or a concrete composition containing coarse aggregate. Good. The paste composition and the mortar composition may be a colorant, a curing agent, a curing accelerator such as calcium chloride, a water reducing agent such as sodium naphthalenesulfonate, a coagulant, carboxymethylcellulose, methylcellulose, polyvinyl alcohol, etc. Various additives such as thickeners, foaming agents, waterproofing agents such as synthetic resin emulsions, and plasticizers may be included.
[0087]
【The invention's effect】
According to the molded product for delaying cement hardening and the kit for producing a surface-decorated concrete product according to the present invention, joint grooves having a certain depth can be easily and efficiently formed between the decorative materials of the surface-decorated concrete product. Moreover, the surface decoration work after concrete hardening can be simplified and a beautiful surface decoration concrete product can be obtained easily. Furthermore, the surface decoration of the concrete product can be easily performed regardless of the type of decorative material and the decorative design.
[0088]
According to the method for producing a molded product for retarding cement hardening and the method for producing a kit for producing a surface-decorated concrete product according to the present invention, it is possible to easily and efficiently produce an excellent molded product and kit as described above.
[0089]
Moreover, according to the manufacturing method of a surface decoration concrete product, while being able to manufacture a highly decorative product simply and efficiently, it is excellent in versatility.
[0090]
【Example】
Examples Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
[0091]
Example 1
Polyoctenylene polymer (VESTENAMER 5031; manufactured by HULS AG) 100 parts by weight, 70 parts by weight of citric acid pulverized to an average particle size of 100 μm or less, 30 parts by weight of calcium carbonate, and 2 parts by weight of calcium stearate under conditions of 120 ° C. After mixing with a kneader, the mixture was pulverized with a crusher to obtain granules having an average particle diameter of 2 to 3 mm. After 100 parts by weight of these granules were dry blended with 3 parts by weight of the blowing agent toluene sulfonyl hydrazide (manufactured by Eiwa Kasei Co., Ltd .; Unihole NH500) and 0.3 parts by weight of calcium stearate, the resin temperature was 140 ° C. using an extruder. Extrusion was performed under the above conditions to obtain a foam sheet having a width of 35 cm and a thickness of 5 mm. The average foaming ratio of the obtained foamed sheet was 2.3.
[0092]
Separately, the same operation as described above was performed except that no foaming agent was used, and a non-foamed sheet was prepared. The non-foamed sheet has a tensile modulus of 18,000 kgf / cm.²The tensile breaking elongation was 24%.
[0093]
The foam sheet is cut into a size of 30 cm in width and 55 cm in length, and 25 tiles having a size of 5 cm × 10 cm and a thickness of 1 cm are placed on the foam sheet, and the longitudinal direction of the tile is aligned with the longitudinal direction of the sheet. The surface was arranged in contact with the foam sheet. The tiles were separated from the end of the foam sheet by 5 mm and arranged in 5 rows each in the width and longitudinal direction of the foam sheet at an interval of 1 cm. Next, the tile was press-fitted into the foamed sheet by a flat plate press through a rubber sheet having a thickness of 5 mm to a depression depth of 2 mm. The sheet on which the tiles were arranged in this manner was used as a unit tile, and two sheets were laid side by side on the bottom of a mold frame of 60 cm × 55 cm and a depth of 10 cm. Concrete was placed on the unit tiles, subjected to curing treatment at 50 ° C. for 24 hours, and further allowed to stand at room temperature for 24 hours, and then demolded. After demolding, the foam sheet was removed, and while applying pressurized water, the tile surface and tile joint grooves were removed from the tile. In about 2 minutes of the removal operation, the “loose” was removed almost without leaving, and a tile-decorated PC board having a good surface finish and having joint grooves with an average depth of 3 mm was obtained.
[0094]
Example 2
In an autoclave having a capacity of 10 liters equipped with a stirring blade, 3452 g (35.2 mol) of maleic anhydride and 2539 g (40.9 mol) of ethylene glycol were added, hydroquinone as a polymerization inhibitor, and tetra-n as a polymerization catalyst. -Butoxy titanium was added so that content might be 100 ppm and 50 ppm, respectively. In order to stir the contents and remove the water generated by the reaction, the temperature was raised from normal temperature to 150 ° C. over 3 hours while flowing nitrogen gas, and further from 150 ° C. to 210 ° C. over 24 hours. The temperature was raised and the reaction was stopped. 3 parts by weight of an organic peroxide (manufactured by NOF Corporation; perbutylo), 0.005 part by weight of cobalt acetate as a crosslinking catalyst, with respect to 100 parts by weight of the obtained oily unsaturated polyester (weight average molecular weight 2250), After adding 3 parts by weight of toluene sulfonyl hydrazide as a blowing agent (manufactured by Eiwa Kasei Co., Ltd .; Unihole NH500) and 30 parts by weight of calcium carbonate and mixing them, the resulting mixture was formed into a film of polyethylene terephthalate having a thickness of 30 μm. The film was applied to a thickness of 2 mm and immediately heat-treated for 7 minutes in an electric oven at 120 ° C. The applied unsaturated polyester was cured while foaming, and a foamed sheet having a thickness of about 5 mm was obtained.
[0095]
Separately, a non-foamed sheet was prepared by the same operation as described above except that no foaming agent was used. This non-foamed sheet has a tensile modulus of 48,000 kgf / cm.²The tensile breaking elongation was 5%.
[0096]
The foamed sheet was cut into a size of 60 cm × 55 cm, and 25 tiles having a size of 5 cm × 10 cm and a thickness of 1 cm were arranged on the sheet in the same manner as in Example 1. Next, the tile was pressed from the back side of the tile into a foam sheet by a flat plate press so that the depression depth of the foam by the tile was 3 mm. Thus, the sheet | seat in which the tile was arrange | positioned was installed in the bottom part of the formwork of 60 cm x 55 cm and depth 10cm as a unit tile. Concrete was placed on the unit tiles, subjected to curing treatment at 50 ° C. for 24 hours, and further allowed to stand at room temperature for 24 hours, and then demolded. After demolding, the foam sheet was removed, and while applying pressurized water, the tile surface and tile joint grooves were removed from the tile. The “noro” was easily washed away, and a tile-decorated PC board having an extremely beautiful appearance was obtained without remaining on either the tile surface or the joint groove. The time required for removing “Noro” was about 2 minutes. Moreover, the average depth of the joint groove was 5 mm.
[0097]
Example 3
Unsaturation obtained in the same manner as in Example 2 except that the monomer formulation was 3136 g (32.0 mol) maleic anhydride, 531 g (3.2 mol) terephthalic acid, and 2538 g (40.9 mol) ethylene glycol. 100 parts by weight of polyester (weight average molecular weight 2200), 20 parts by weight of diethylene glycol monoacrylate, 3 parts by weight of organic peroxide (manufactured by NOF Corporation; perbutylo), 0.005 part by weight of cobalt acetate as a crosslinking catalyst, foaming 3 parts by weight of toluene / sulfonyl hydrazide (manufactured by Eiwa Chemical Co., Ltd .; Unihole NH500) and 5 parts by weight of calcium carbonate were added and mixed, and the resulting mixture was added to a 30 μm thick polyethylene terephthalate film to a thickness of 500 μm. Immediately after application for 1 minute in an electric oven at 150 ° C. Heat treated. The applied unsaturated polyester was cured while foaming, and a foamed sheet having an average thickness of 1.2 mm was obtained.
[0098]
Separately, a non-foamed sheet was prepared by the same operation as above except that no foaming agent was used. The non-foamed sheet has a tensile modulus of 12,000 kgf / cm.²The tensile breaking elongation was 65%.
[0099]
A unit tile was produced in the same manner as in Example 2 except that each tile was pressure-bonded to the foam sheet via a 1 cm square double-sided adhesive tape using the foam sheet. However, the depression depth of the tile was not set, and the tile was pressed with the total load of the flat plate press set to 2 tons. The foam sheet was slightly plastically deformed and depressed in the pressing portion, and the foam sheet in the portion corresponding to the joint between the tiles was slightly raised. Using the unit tile thus obtained, concrete pouring, curing, demolding, and removal of the foamed sheet were carried out in the same manner as in Example 2, and then “Shiro” was washed. All of the “slope” on the tile surface could be easily removed, and a tile-decorated PC board with extremely shallow joint grooves was obtained. The joint groove has a concave curved surface shape, and the depth was 1 to 1.5 mm.
[0100]
Example 4
To 100 parts by weight of pellets of polystyrene (Asahi Kasei Polystyrene GP666; manufactured by Asahi Kasei Co., Ltd.), 1 part by weight of a foaming agent azodicarbonamide (manufactured by Sankyo Kasei Co., Ltd .; Cellmic C), 10 parts by weight of calcium carbonate, 1 part by weight of calcium stearate Part was added, mixed and extruded to produce a foam sheet having a width of 35 cm and a thickness of 5 mm.
[0101]
Separately, a non-foamed sheet having a thickness of 2 mm was prepared by the same operation as described above except that the foaming agent was not used. This non-foamed sheet has a tensile modulus of 38,000 kgf / cm.²The tensile breaking elongation was 18%.
[0102]
On one side of the foamed sheet, 100 parts by weight of unsaturated polyester obtained in the same manner as in Example 3, 20 parts by weight of diethylene glycol monoacrylate, 3 parts by weight of an organic peroxide (manufactured by NOF Corporation; perbutylo) and crosslinking A mixture of 0.005 parts by weight of cobalt acetate as a catalyst was added at 100 g / m 2.²The coating amount was set so that the coating amount was 1 ° C., and heat treatment was performed in an oven at 150 ° C. for 1 minute. The foamed sheet coated with the concrete-retarded unsaturated polyester thus obtained is cut into a size of 30 cm × 55 cm, with the coated surface at the top, 60 cm × 55 cm, and 10 cm deep at the bottom of the formwork. Place two tiles side by side and arrange 25 tiles of 5 × 10 cm and 1 cm thickness on the foam sheet in the same manner as in Example 1, apply pressure from the back, and sequentially place each tile in the foam sheet, The indentation depth was 3 mm. Next, concrete was placed, cured, demolded, and the foamed sheet was removed by the same operation as in Example 1, and then “Noro” was washed with pressurized water. In about 2 minutes of the removal operation, all of the “loose” was removed, and a tile-decorated PC board having a good surface finish and having joint grooves with an average depth of 5 mm was obtained.
[0103]
Comparative example
A braided sheet of polypropylene stretched yarn coated with an adhesive is cut into a size of 30 cm x 55 cm, and tiles of 5 cm x 10 cm and a thickness of 1 cm are arranged on the sheet at an interval of 1 cm so that the surface is in contact with the adhesive. And created unit tiles. These two unit tiles are placed on the bottom of a 60cm x 55cm, 10cm deep formwork so that the tiles are on the top surface, and each of the joints is cut to have a cross section of 11mm x 5mm in advance. The polyurethane was packed using a spatula while carefully removing the gaps. The time required for this stuffing operation was about 10 minutes. Next, concrete was cast from the back of the tile and cured and demolded in the same manner as in Example 1 to prepare a PC board. The polypropylene sheet and the padding were removed, and the “noro” washes with water using tools such as a spatula, a wire brush, and an electric wire brush. It took nearly 30 minutes to remove almost all of “Noro” including joint grooves.

Claims (20)

A molded article for cement hardening delay comprising a porous body that can be indented by pressing and having cement hardening retarding ability , wherein the porous body has a tensile elongation at break of 0 to 80% and a tensile elastic modulus A porous body composed of a resin composition of 8000 to 300,000 kgf / cm ² or a non-woven fabric having a bulk density of 0.1 to 0.8 g / cm ³ and having a cement hardening retarding ability (1 ), Or a porous body in which a curing retardation layer (2) having cement hardening retardation is formed on the surface of the porous body, and the porous body (1) having the cement hardening retardation or the curing retardation layer ( 2) A molded article for cement hardening delay comprising a resin capable of developing a cement hardening retarding ability by hydrolysis or a resin having a phosphonic acid group, or containing a cement hardening retarder .   The molded article for cement hardening delay according to claim 1, which is formed in a sheet shape.   The molded article for delaying cement hardening according to claim 2, which has a base sheet layer on one surface. The resin composition according to claim 1 cement delay molded article further comprising an inorganic powder. Claim 1 cement delay molded article according cement set retarding ability expressible resin is an unsaturated polyester by hydrolysis. The unsaturated polyester is a polyvalent carboxylic acid component containing an unsaturated polyvalent carboxylic acid having 4 to 6 carbon atoms in the main chain or a derivative thereof, and a polyhydric alcohol having 2 to 4 carbon atoms in the main chain or a condensate thereof. The molded article for delaying cement hardening according to claim 5, which is an unsaturated polyester obtained by a reaction with a polyol component containing. The molded article for cement hardening delay according to claim 6 , wherein the polyvalent carboxylic acid component further contains an aromatic dicarboxylic acid or a derivative thereof. The molded article for cement hardening delay according to claim 5 , wherein the unsaturated polyester is a cured product by crosslinking. The molded article for cement hardening delay 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. The cement setting retarder is at least one selected from phosphoric acid or a salt thereof, boric acid or a salt thereof, hexafluorosilicate, phosphonic acids, oxycarboxylic acids, keto acids, polyhydric phenols, lignin sulfonic acids and saccharides claim 1 cement delay molded article wherein the species. The molded article for cement hardening delay according to claim 1 , comprising a porous body (1) having cement hardening retarding ability or a porous body having a surface on which a hardening delay layer (2) having cement hardening retarding ability is formed. A method for producing a cement hardening delay-molding product comprising a step of foam-molding a resin composition having a tensile elongation at break of 0 to 80% and a tensile elastic modulus of 8000 to 300,000 kgf / cm ² to form the porous body. Manufacturing method. The method for producing a molded article for delaying cement hardening according to claim 11, wherein a resin composition having a tensile elongation at break of 20 to 80% and a tensile modulus of elasticity of 8000 to 20000 kgf / cm ² is foam-molded. The method for producing a molded article for delaying cement hardening according to claim 11, wherein a resin composition having a tensile elongation at break of 0 to 30% and a tensile elastic modulus of 10,000 to 300,000 kgf / cm ² is foam-molded. The method for producing a molded article for delaying cement hardening according to claim 11 , wherein the resin composition is foamed at a foaming ratio of 1.5 to 80 times. The method for producing a molded article for delaying cement hardening according to claim 11 , comprising foaming and molding the resin composition containing the unsaturated polyester and curing the unsaturated polyester by heating. The molded article for cement hardening delay according to claim 1 , comprising a porous body (1) having cement hardening retarding ability or a porous body having a surface on which a hardening delay layer (2) having cement hardening retarding ability is formed. A method for producing a molded article for delaying cement hardening, which comprises a step of forming a porous body composed of a nonwoven fabric having a bulk density of 0.1 to 0.8 g / cm ³ by making fibers. The surface of claim 1 wherein the cement set retarding molded article, by holding by invagination or depressed by pressing the decorative material, the surface wherein the decorative material is arranged decorative concrete products manufacturing kit. 18. The kit for producing a surface-decorated concrete product according to claim 17 , wherein the decorative material is attached to the cement hardening delay molding with an adhesive or an adhesive. Claim 1 presses the decoration material on the surface of the cement retardative molded article according, by holding the decorative material is recessed or depressed the molded article, the surface decorative concrete products for disposing the decorative material Manufacturing method of manufacturing kit. A molding material for delaying cement hardening, which is provided with a decorative material on its surface, is formed by pressing a decorative material into the molded product for delaying cement hardening according to claim 1 and holding it. A method for producing a surface-decorated concrete product, in which a decorative material is disposed so as to be positioned inside, an inorganic curable composition is placed and cured, and then a mold and a molded product for retarding cement hardening are removed.