JPH08309717A - Film for delaying curing of cement and its preparation - Google Patents

Abstract

PURPOSE: To accurately form a pattern and a washed face on the surface of a concrete product and to improve decorative properties by feeding a mortar compsn. and washing the curd face. CONSTITUTION: A film with delaying ability for curing of cement and pressure- sensitive adhesive properties is arranged in a frame and a decorative material such as a tile is sticked on the pressure-sensitive adhesive face of the film and a cement concrete compsn. is fed. A decorative finished concrete product is obtd. by washing the surface of the cured concrete and removing the uncured part. As the film for delaying curing of cement, a film (A1) formed of a resin (1) with delaying ability for curing of cement such as unsatd. polyester resin, a film (A2) contg. a cement curing retarder (2) such as phosphonic acid compd. and oxycarboxylic acids, a film (A3) in which a curing delaying layer is formed on a base film and these films (A4) the surface of which a pressure-sensitive adhesive layer or an adhesive layer is formed, are included. As a specified pattern is formed by cutting the curing delaying layer, it may be peelable to the base film.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a film useful for delaying the curing of the surface of a curable composition containing cement and a method for producing the film. More specifically, the present invention relates to a film useful for washing out an uncured portion of concrete, exposing an aggregate or forming an uneven pattern on the surface of a concrete product, and a method for producing the film. Further, the present invention relates to a pressure-sensitive adhesive sheet for unit tile that is useful for constructing tiles on the surface of concrete, a unit tile using this pressure-sensitive adhesive sheet, and a method for manufacturing a precast concrete board using this unit tile.

[0002]

2. Description of the Related Art For the construction of tiles on the surface of concrete, there has been proposed a method of using unit tiles in which a plurality of tiles are adhered and arranged on the surface of an adhesive layer of an adhesive tape. In the method using this unit tile, place the unit tile in the formwork where concrete is placed,
After pouring concrete into the formwork and curing it, demolding,
After exposing the tile to the surface by removing the adhesive sheet, the tile is installed by wrapping around the surface of the tile to remove the hardened cement and finishing the surface. This surface finishing is a process that is indispensable for the construction of tiles characterized by a beautiful surface, since the hardened cement adhering to the tiles is often shaved by hand. However, the work of removing the hardened cement adhering to the tile is time-consuming, troublesome, and complicated, and not only the tile construction cost rises, but also the work of removing the hardened cement causes damage to the tile surface.

Cement hardening retarders are used to process the surface of concrete products and to form patterns on the surface. For example, a concrete washing plate is a mold coated with a cement retarder, or a mold in which a paper impregnated with the retarder is laid, and after pouring the mortar composition, a mortar composition for lining. It is manufactured by casting an object and curing it, curing the mortar composition, removing the mold, and washing the concrete surface to which the curing retarder is attached.

In JP-A-5-38711 and JP-A-5-50411, a mixture containing an ultra-retardant, a tackifier, an extender and a white pigment is adhered to the inner surface of a mold to form a mortar or concrete. A method is disclosed in which the surface of a cement product is finished by casting, curing and demolding, washing out the cement paste on the surface of the cement product that contacts the mold. Also, as a method for forming an uneven pattern on the surface of a concrete product, a method using a cement hardening retarder and a method using a paper pattern impregnated or coated with the cement hardening retarder are known. For example, JP
In JP-A 3-216703, a step of cutting the pattern paper to produce a cutting pattern paper corresponding to a pattern such as a predetermined character or a figure, a step of adhering the cutting pattern paper to a predetermined portion on the inner surface of the mold frame, A predetermined rugged pattern is formed on the surface of the concrete product through the steps of placing the mortar composition on the surface, curing it, removing the formwork to take out the concrete product, and washing the pattern part of the concrete product. are doing. Japanese Unexamined Patent Publication No. 61-202803 discloses a method in which a tile or the like is attached to paper coated with the cement retarder, set in a mold, and washed out in the same manner as above. Further, in the method of using a cement hardening retarder instead of the pattern paper, a step of drawing a predetermined pattern on the mold using the hardening retarder, a step of placing mortar in the same manner as described above and taking out from the mold, a pattern was formed. The pattern is formed by going through the step of washing the uncured surface corresponding to the part.

However, the pattern paper which is impregnated or coated with the cement hardening retarder has low strength against the placement of the mortar composition. Therefore, the pattern paper is torn or the position of the template is displaced, and it is difficult to form a washout surface or a pattern on a predetermined portion of the concrete product. Furthermore, when a conventional set retarding type washout agent that suppresses the hydration mechanism of cement is used, the set retarder dissolves in the water in the cement concrete. Therefore, with the bleeding phenomenon due to the increase of excess water in the cement concrete, the curing retardant dissolved in water moves upward along the mold surface, so that the curing is delayed only in the part that does not need to be washed out. On the other hand, on the surface through which the bleeding water has passed, the washout depth becomes particularly deep. Therefore, it is not suitable as a makeup method for concrete products. Further, in order to form the graphic pattern, it is necessary to cut the pattern paper into a predetermined shape and size and fix it to the mold frame with an adhesive. Therefore, it is difficult to form a complicated wash-out surface or a pattern, and when forming a pattern on a large amount of concrete products, the work is complicated and the productivity of the concrete products is reduced. On the other hand, when the cement retarder is directly applied to the mold, it takes time to dry or cure the retarder, which not only reduces productivity but also makes uniform coating difficult.
The thickness of the hardening retardation layer of the concrete product varies, which makes it difficult to form a constant washout surface or pattern on the surface of the concrete product.

In Japanese Patent Laid-Open No. 3-224953, a decorative material such as tiles or stones is arranged on a bottom plate of a mold via an embedded embedding agent (concrete non-hardening agent), and concrete is placed. There is disclosed a method for producing a concrete block which is integrated with a decorative material by removing the embedding agent on the surface of a concrete product by washing with water after curing and removing the mold. Japanese Patent Application Laid-Open No. 3-175003 discloses that a decorative material is temporarily attached to the inner surface of a form via an uncured coating material layer, concrete is cast and hardened, and then the mold is removed to remove the surface of the concrete product. Disclosed is a method of producing a concrete product having a surface-decorated surface by removing uncured coating material and uncured portion of concrete by washing with water. This prior document describes that the uncured coating material layer is formed of a mixture of an alkali swelling material such as polyester and polyvinyl alcohol and a super absorbent polymer.

However, even with the methods described in these documents,
Since it is necessary to inject a non-curing agent or a non-curing coating material or to apply a non-curing 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 film.

[0008]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to prevent the occurrence of breakage and displacement even when the mortar composition is cast, and to cure the contact surface side with the mortar composition. It is an object of the present invention to provide a hardening retardation film capable of uniformly suppressing the above phenomenon and accurately forming a pattern or a wash-out surface on the surface of a concrete product, and a manufacturing method thereof.
Another object of the present invention is to provide a film for curing retardation capable of easily and efficiently forming a pattern or a wash-out surface on the surface of a concrete product, and a method for producing the film. Still another object of the present invention is to provide a film which can be easily formed even on a surface of a concrete product even if it has a complicated pattern and can enhance decorativeness, and a method for producing the film. Another object of the present invention is to provide a film useful for obtaining a decorative concrete product by decorating the surface with a decorative material and the like, and a method for producing the film. Still another object of the present invention is to use a pressure-sensitive adhesive film for a decorative material kit, which can easily and efficiently finish the surface of a decorative material such as a tile, and which does not damage the decorative material. An object of the present invention is to provide a decorative material kit film such as a unit tile, and a method for producing a decorative finished concrete product such as a precast concrete board using the decorative material kit film.

[0009]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a film having a retarding ability (inhibiting ability) with respect to hardening of cement, and also having tackiness or adhesiveness. When using, it is possible to stick decorative materials such as stones and tiles by using adhesiveness or adhesiveness, and to form a uniform washout surface and pattern on the concrete surface, so that a concrete product with high decorativeness can be obtained. Found
The present invention has been completed.

That is, the film for retarding cement hardening of the present invention has the ability to delay cement hardening, and also has tackiness or adhesiveness. The film may be a film (A1) composed of a resin (1) having a cement hardening retarding ability or a film (A2) containing a cement hardening retarder (2). Such a film (A1) (A
In 2), the tackiness or adhesiveness can be imparted by the tackiness agent or the adhesive agent contained in the film, or the tackiness agent or the adhesive agent applied to the film. In another aspect of the present invention, a resin (1) having a cement hardening retarding ability on the surface of a base film
Alternatively, it includes a film (A3) having a set retardation layer containing the cement set retarder (2). The curing retardation layer may be peelable from the base film. In the film, tackiness or adhesiveness may be imparted by the base film, or tackiness or adhesiveness may be imparted by the pressure-sensitive adhesive or adhesive contained in the curing retardation layer. That is, it may be an adhesive film in which the surface of the film is provided with adhesiveness. In yet another aspect of the invention,
It also includes a film (A4) having a pressure-sensitive adhesive layer or an adhesive layer formed on the surface of the film, for example, the curing retardation layer. The pressure-sensitive adhesive layer or the adhesive layer can be formed in a form in which the curing retarding component can leach out.

The above-mentioned film for retarding cement hardening has various embodiments depending on the structure of the film, for example, (B1) a resin composition containing a resin (1) having an ability to delay cement hardening and an adhesive or an adhesive. Film forming method, (B2) Cement hardening retarder (2), film forming method of resin composition containing pressure sensitive adhesive or adhesive, (B3) Base film having cement hardening retarding ability on the surface thereof A method for forming a hardening retardation layer containing a resin (1) or a cement hardening retarder (2) and an adhesive or an adhesive, (B4) a resin (1) having a cement hardening retarding ability on the surface of a base film Alternatively, it can be produced by a method of applying a coating liquid containing the cement hardening retarder (2) and forming an adhesive layer or an adhesive layer on the formed hardening retardation layer.

Furthermore, the decorative material kit film of the present invention has a plurality of decorative materials adhered to the adhesive surface or the adhesive surface of the film having adhesiveness or adhesiveness continuously or in a scattered manner in the surface direction. There is. After disposing this decorative material kit film in a mold and casting and curing the inorganic curable composition,
Remove the mold, remove the sticky or adhesive film,
By washing the surface of the exposed decoration material, a decorative concrete product can be efficiently manufactured.

In the present specification, the term "film" means a two-dimensional structure regardless of its thickness and includes a sheet. Further, "adhesive or adhesive" is generically referred to as "adhesive", "adhesive layer or adhesive layer" is generically referred to as "adhesive layer", and "adhesiveness or adhesiveness" is generically referred to as "adhesive". Sometimes referred to as "sex". Further, unless otherwise specified, the term “cement” means an inorganic substance that exhibits a hardening property when mixed with water, and is used to include a pneumatic cement, a hydraulic cement and the like. Further, 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”.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION In the film for retarding cement hardening of the present invention, the cement hardening retarding ability is a resin (1) or a cement hardening retarder (2) having cement hardening retarding ability.
Can be imparted by forming a film containing a composition containing the above-mentioned resin, applying a composition containing the resin (1) or the cement hardening retarder (2), etc. It can be applied by applying a pressure-sensitive adhesive or an adhesive. The film for delaying cement hardening of the present invention, which has tackiness or adhesiveness, may be a film (A1) composed of a resin (1) having a cement hardening delaying ability, and a film containing a cement hardening retarder (2). It may be (A2). In addition, a film (A
1) does not need to contain the set retarder (2), but may contain the cement set retarder (2).

[Cement hardening retardation film (A1)] The cement hardening retardation resin (1) which constitutes the cement hardening retardation film (A1) has a film forming ability and a retarding or suppressing effect on the hardening of cement. It is not particularly limited as long as it has a resin, and examples thereof include unsaturated polyester resins, vinyl ester resins such as epoxy (meth) acrylate, and resins having a phosphonic acid group. These resins may be used alone or in combination of two or more. Of these resins, unsaturated polyester resins are preferred. The unsaturated polyester resin can be obtained by subjecting a reaction component containing glycol and maleic anhydride (or maleic acid) as main components to a dehydration condensation reaction.

As the glycol, ethylene glycol, propylene glycol, 1,3-butanediol,
Alkylene glycols such as tetramethylene glycol, hexanediol and neopentyl glycol; diethylene glycol, triethylene glycol, polyethylene glycol (hereinafter, simply referred to as polyethylene glycol unless otherwise stated), dipropylene glycol, tripropylene xerycol, Examples thereof include polypropylene glycol (hereinafter, simply referred to as polypropylene glycol unless otherwise specified), polyoxyalkylene glycol such as polytetramethylene glycol, and the like. These glycols may be used alone or in combination. A preferable glycol is a polyoxyalkylene glycol selected from polyethylene glycol and polypropylene glycol as a main component (for example, 50 to 1 of the total glycol component).
00% by weight). The glycol component containing propylene glycol or polypropylene glycol is useful for imparting flexibility and hydrophilicity and enhancing solubility with a diluent (polymerizable monomer) such as styrene or an acrylic monomer. The molecular weight of the polyoxyalkylene glycol is, for example, a weight average molecular weight of 100 to 750.
0, preferably about 200 to 5000, and 200 to
It is often around 2500.

The unsaturated polyester resin may be modified with a component other than the glycol and maleic anhydride in order to adjust the properties such as strength, elongation, flexibility, flexibility and resistance of the film. For example, in addition to at least one component of the polyoxyalkylene glycol and maleic anhydride, other diol (for example, alkylene glycol such as ethylene glycol and propylene glycol), polyhydric alcohol (for example, glycerin, trimethylolpropane, penta Erythritol, etc.), aliphatic polycarboxylic acids (eg, itaconic acid, adipic acid, azelaic acid, sebacic acid, etc.), aromatic polycarboxylic acids (eg, phthalic acid, phthalic anhydride, terephthalic acid, trimellitic acid, etc.) ) Etc. can be copolymerized. Although the molecular weight of the unsaturated polyester resin is not particularly limited, for example, the weight average molecular weight is 300 to 25,000, preferably about 500 to 15,000.

The unsaturated polyester resin or vinyl ester resin may be formed into a film as it is, but it is usually mixed with a reactive diluent to form a film. As the reactive diluent, a polymerizable vinyl monomer, for example, a styrene-based monomer such as styrene, an alkyl group such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate having a carbon number of about 1 to 10 is used. Examples thereof include monomers having a functional group such as alkyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acrylic acid, and glycidyl (meth) acrylate. These polymerizable monomers may be used alone or in combination of two or more. The amount of the reactive diluent used can be selected according to the desired characteristics of the film, and is, for example, 10 to 500 parts by weight, preferably 25 to 20 parts by weight with respect to 100 parts by weight of the resin.
It is about 0 parts by weight.

The film of unsaturated polyester resin or vinyl ester resin can be obtained by polymerizing and curing with a polymerization initiator such as an organic peroxide. Examples of the organic peroxide include methyl ethyl ketone peroxide, cumene hydroperoxide, benzoyl peroxide, t-butyl peroxybenzoate, t-
Butyl peroxy-2-ethyl hexanoate, dicumyl peroxide, etc. are mentioned. The unsaturated polyester resin or vinyl ester resin can be cured at room temperature, but in order to cure the unsaturated polyester resin or vinyl ester resin in a short time (for example, about 0.5 to 50 minutes), it is advantageous to perform the temperature at about 60 to 200 ° C. Is. To accelerate the curing, if necessary, a curing accelerator, for example, an organic acid salt of cobalt such as cobalt naphthenate and cobalt octylate, β-diketones such as acetylacetone and ethyl acetoacetate, and aromatic tertiary amines. , A mercapto compound and the like may be used in combination.

[Curing retardation film (A2)] The second curing retardation film (A2) of the present invention contains a curing retarder (2), and is usually used together with the curing retarder (2). And a resin having. As the resin, the resin (1) having the curing retarding ability that constitutes the film (A1) may be used, but a resin having a film forming ability other than the resin (1) is often used. The type of the cement setting retarder (2) is not particularly limited as long as it is a setting retarder or a setting retarder that reduces the setting speed of cement, and an inorganic or organic setting retarder can be used. The inorganic curing retarder includes phosphoric acid, boric acid or salts thereof, hexafluorosilicate, and the like.

Examples of the organic curing retarder include phosphonic acid compounds having a phosphon group PO ₃ H ₂ and non-phosphonic acid compounds as shown below. Phosphonic acid type curing retarder aminodi (methylenephosphonic acid), aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-
Diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid) or salts thereof.

Examples of the salt include salts with ammonia, alkali metals such as sodium and potassium, and alkaline earth metals such as calcium, magnesium and barium. Examples of salts of phosphonic acid compounds include aminotri (methylenephosphonic acid) pentasodium salt, 1-hydroxyethylidene-1,1-diphosphonic acid tetrasodium salt, ethylenediaminetetra (methylenephosphonic acid) calcium sodium salt, and hexamethylenediamine. Examples thereof include tetra (methylenephosphonic acid) potassium salt, diethylenetriamine penta (methylenephosphonic acid) sodium salt, and the like.

Non-phosphonic acid type curing retarder Glycolic acid, lactic acid, malic acid, tartaric acid, citric acid, gluconic acid and other oxycarboxylic acids 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 copolymers, polyacrylic acid, polymethacrylic acid, styrene- ( Meta)
Acrylic acid copolymer, (meth) acrylic acid ester-
(Meth) acrylic acid copolymers, homopolymers or copolymers of monomers having a carboxyl group such as ethylene sulfonic acid-acrylic acid copolymers, or salts thereof (preferably low molecular weight polymers or salts thereof); antioxidants (eg, , Ascorbic acid, isoascorbic acid, etc.); polymers, eg 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 can be mentioned.

Of these curing retarders, phosphonic acid compounds, oxycarboxylic acids, polycarboxylic acids, homopolymers or copolymers of monomers having a carboxyl group, isoalcorbic acid, phosphoric acid, boric acid or salts thereof. , At least one component selected from the group consisting of polyhydroxysilane and hexafluorosilicate is preferred. As the curing retarder, a phosphonic acid compound, a hydroxycarboxylic acid, a polycarboxylic acid (polycarboxylic acid), isoalcorbic acid or a salt thereof, polyhydroxysilane, etc. are often used. A combination with a carboxylic acid is preferred. Such combinations include, for example, the combination of aminotri (methylenephosphonic acid) and citric acid. The ratio of the phosphonic acid compound and the hydroxycarboxylic acid is, for example, the former / the latter = 1
00 / 25-500 (weight ratio), preferably 100/5
It is about 0 to 250 (weight ratio). Further, a preferable curing retarder has an acidic group (for example, a phosphonic acid group, a carboxyl group, a sulfonic acid group, etc.) or a salt thereof, and is often water-soluble. One or more curing retarders can be used.

The type of resin having film forming ability is not particularly limited, and various thermoplastic resins and thermosetting resins can be used. Examples of the thermoplastic resin having film forming ability include 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, Nylon 66, Nylon 610, Nylon 612, Nylon 11, Nylon 1
Polyamides such as 2; vinyl ester resins such as polyvinyl acetate, ethylene-vinyl acetate (EVA) copolymer, vinyl acetate-vinyl versatate copolymer (VA-VeoVa); polyvinyl alcohol, ethylene-vinyl alcohol copolymer Saponification products of vinyl ester resins such as polymer; ethylene-ethyl acrylate copolymer, ethylene- (meth) acrylic acid copolymer; polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinylidene chloride-vinyl acetate copolymer Polymers, halogen-containing polymers such as polychloroprene; acrylic resins, acrylic polymers such as styrene- (meth) acrylic acid ester copolymers; polystyrene, styrene-butadiene copolymers, styrene-butadiene-acrylonitrile copolymers, etc. Styrenic polymer; methyl Cellulose, hydroxyethyl cellulose, cellulosic polymers such as cellulose acetate; and natural polymers. Among thermoplastic resins, rubbery polymers (for example, styrene-butadiene rubber (SB
R), chloroprene rubber (CR) and the like can be used as a latex and can be produced by emulsion polymerization of a thermoplastic resin (for example, ethylene-vinyl acetate copolymer (EVA),
Acrylic resin, etc.) can be used as an emulsion.
In addition, EVA may be used as a re-emulsifying powder resin.

Examples of the thermosetting resin include thermosetting acrylic resin, unsaturated polyester resin, vinyl ester resin, diallyl phthalate resin, epoxy resin, urea resin and phenol resin.

These resins may be used either individually or in combination of two or more. Further, a thermoplastic resin is often used as the resin having film forming ability. In particular, a preferable resin is often a hydrophilic resin (for example, a water-soluble or water-dispersible resin) or a hydrophilized resin such as latex or emulsion.

The amount of the setting retarder (2) can be selected within a range capable of suppressing the setting of cement and capable of forming a film, and is, for example, 5 to 1000 with respect to 100 parts by weight of the resin.
Parts by weight, preferably 10 to 700 parts by weight, more preferably about 25 to 500 parts by weight, and often about 25 to 400 parts by weight (for example, 50 to 300 parts by weight).

[Adhesive retardation film (A
1) (A2)] In the film (A1) (A2), the adhesiveness or adhesiveness is determined by the inclusion of the adhesive in the film (A1) or (A2), or the surface of the film (A1) (A2). It can be applied by forming the pressure-sensitive adhesive layer. In the film containing an adhesive (A1) (A2), the content of the adhesive may be a range that can impart tackiness to the film and does not deteriorate the characteristics of the film, for example, a resin having a curing retarding ability. (1) 10 to 500 parts by weight, preferably 25 to 400 parts by weight, more preferably 50 to 300 parts by weight, and often 25 to 250 parts by weight, relative to 100 parts by weight. In the films (A1) and (A2) having a pressure-sensitive adhesive layer formed on the surface, the pressure-sensitive adhesive layer can be configured in the same manner as the pressure-sensitive adhesive layer or the adhesive layer of the film (A4) described later.

[Manufacturing Method of Films (A1) and (A2) for Curing Retardation] The film (A1) composed of the resin (1) having a curing retarding ability is a conventional film forming method (extrusion) depending on the kind of the resin. It can be obtained by a molding method, a casting method, a calendering method, etc., and is often manufactured using the casting method. When a resin having a phosphonic acid group is used, it is usually used as an organic solvent solution in many cases. Examples of the organic solvent include alcohols such as ethanol and isopropanol, aliphatic hydrocarbons such as hexane and octane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons and petroleum. System solvents, ketones such as acetone and methyl ethyl ketone, ethers, esters such as ethyl acetate,
These mixed solvents etc. are mentioned. When the casting method is adopted, a film can be obtained by applying the resin composition on a smooth surface of a support, drying or curing it, and then peeling the coating film from the support. As the support having a smooth surface, various belts (for example, stainless belts, urethane resin belts, surface-treated iron belts, etc.), films (for example, polyester film, polypropylene film, etc.), drums, etc. can be used. .
In order to enhance the peelability of the coating, the surface of the support is coated with a silicone compound such as silicone oil or silicone resin,
The surface tension of the support may be reduced by surface treatment with a liquid fluorine-containing compound or a fluorine-based compound such as a fluororesin.

The film containing the curing retarder (2) is
It can be obtained by subjecting a resin composition containing a curing retardant and a resin to a conventional film forming method in the same manner as the film (A1) depending on the type of resin. In that case, you may use the said organic solvent according to the kind of resin. When using the resin latex or resin emulsion, it is not necessary to use a solvent. The film formation may be carried out by an extrusion molding method, but when the thermoplastic resin is used in the form of a latex and / or emulsion capable of forming a film, the curing retarder is not excessively heated,
There is an advantage that a film can be obtained by the casting method.

The thickness of the hardening retardation films (A1) and (A2) can be selected within a range that does not impair workability, mechanical strength, etc., for example, 15 to 500 μm, preferably 20 to 30.
0 μm, more preferably about 30 to 200 μm, and often about 50 to 200 μm. When the thickness of the film is small, the strength is lowered and it may not be possible to maintain a high curing delay property, and when it is too thick, the handleability is likely to be impaired.

[Curing retardation film (A3)] In the third curing retardation film (A3) of the present invention, the resin (1) or the cement curing retarder (having a cement curing retardation ability on the surface of the base film has a cement curing retarding ability. A curing retardation layer (3) containing 2) is formed. This curing retardation layer (3) may have tackiness. The polymer constituting the substrate film is not particularly limited, and examples thereof include olefin polymers such as polyethylene and polypropylene; polyesters such as polyethylene terephthalate and polybutylene terephthalate (particularly polyalkylene terephthalate); ethylene-vinyl acetate copolymer, ethylene- Acrylic acid copolymers; acrylic resins; polystyrene; polyvinyl chloride; polyamides; polycarbonates; polyvinyl alcohol, ethylene-vinyl alcohol copolymers and the like. These polymers may be used alone or in combination of two or more. As the substrate film, a film for curing retardation (A1) composed of the resin (1) having the curing retarding ability or a film (A2) containing a curing retardant (2) may be used. As the base film, for example, a laminated film in which a film made of polyethylene or the like is laminated on one or both sides of a cloth woven of fibers such as polyethylene fibers may be used. Further, the base film may be a film having improved hand tearability and dimensional stability. The base film may be a single film or a composite film in which a plurality of layers are laminated. The base film may be an unstretched film or a uniaxially or biaxially stretched film. Further, the surface of the base material film may be surface-treated by flame treatment, corona discharge treatment, plasma treatment or the like in order to enhance the adhesion to the curing retardation layer (3). The surface tension of the surface-treated base film is about 40.
It is often dyn / cm or more. Curing delay layer (3)
May be peelable from the substrate film. When the curing retardation layer can be peeled from the base film, the predetermined portion or region of the curing retardation layer is cut according to the desired pattern and peeled from the base film, and the film is placed in the mold. By placing an inorganic curable composition (such as a mortar composition), and washing out the contact surface of the cured concrete product with the film,
It is possible to form a wash-out surface in which patterns, aggregates, etc. are exposed at a portion corresponding to the non-cutting portion on the surface of the concrete product. The surface of the substrate film may be untreated in order to make the curing retardation layer peelable, for example, wax,
It may be treated with a releasing agent such as higher fatty acid amide or silicone oil. The surface tension of the base film can be relatively selected in association with the adhesive strength of the curing retardation layer within a range that does not impair the releasability of the curing retardation layer. The surface tension of the substrate film is, for example, 38 dyn / cm or less, preferably 20 to
38 dyn / cm, more preferably 25 to 36 dyn
It is often about / cm.

The hardening retardation layer (3) comprises the resin (1) or the cement hardening retarder (2) having the cement hardening retarding ability.
Is included. The curing retardant resin (1) and the curing retardant (2) capable of forming a coating film may be used alone or in combination to form a curing retardation layer, and the curing retarder (2) is a non-film formation. In the case of having a property, a curing retardation layer may be formed in combination with a binder resin. This binder resin may be a resin having a film-forming ability which constitutes the film (A2) for curing retardation.

Examples of the binder resin include polyvinyl acetate, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, acrylic polymer, polystyrene, styrene-acrylic acid ester copolymer, polyester. , Polyacetal,
Polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyamide, polyurethane, polycarbonate, chlorinated polyolefins such as chlorinated polypropylene, cellulosic polymers such as acetyl cellulose, acetyl butyl cellulose, ethyl cellulose, 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-non-conjugated diene rubber, acrylic rubber, chlorosulfonated polyethylene rubber, silicone rubber, urethane rubber, etc.) Are exemplified. These binder resins may be used either individually or in combination of two or more.

The amount of the binder resin used can be selected depending on the types of the curing retarding resin (1) and the curing retardant (2). When the curing retarding resin (1) is used, the binder resin is not necessarily required, but for example, the binder resin is 0 to 200 parts by weight, preferably 0 to 100 parts by weight with respect to 100 parts by weight of the curing retarding resin (1). It can be selected from the range of about parts by weight. When the curing retardant (2) is used, the ratio of the binder resin and the curing retarder is the same as that of the curing retarding film (A2), that is, the ratio of the curing retarder (2) is, for example, 5 to 1000 parts by weight, preferably 10 to 700, relative to 100 parts by weight of resin
It is about 25 to 500 parts by weight, more preferably about 25 to 500 parts by weight (for example, 50 to 400 parts by weight) in many cases.

[Adhesive retardation film (A
3)] In the film (A3) on which the curing retardation layer (3) is formed, the tackiness is the same as that of the films (A1) and (A2), and the base film contains an adhesive or an adhesive composition described below. It can be applied by a method, a method of incorporating an adhesive or an adhesive composition into the curing retardation layer (3), and the like. In the latter method, a film for curing retardation is obtained in which an adhesive layer containing a curing retarding component is formed on the surface of a substrate film. When the curing delay layer (3) contains a pressure-sensitive adhesive, the proportion of the pressure-sensitive adhesive can be selected within a range in which tackiness is exhibited, and for example, 10 to 500 parts by weight relative to 100 parts by weight of the curing delay layer (3). , Preferably 25 to 400 parts by weight, more preferably 50 to 300 parts by weight, and often 25 to 250 parts by weight.

[Production Method of Film (A3) for Delaying Curing]
The film for curing retardation (A3) is prepared by a conventional method, for example,
A coating liquid containing the curing retardant resin (1) or the curing retardant (2) together with a pressure sensitive adhesive or a pressure sensitive adhesive composition as needed is applied to at least one surface of a substrate film, and dried or cured. Can be manufactured by The coating liquid may contain the same organic solvent as described above. At the time of application, a brush roller, a rubber spatula, etc. may be used, but industrially, application means used for ordinary coating,
For example, a dip coater, roll coater, gravure coater, air knife coater, reverse roll coater, comma coater, bar coater, curtain coater, spray, etc. are often used.

In such a film for curing retardation (A3), the thickness of the base film is, for example, 10 to 200 μm.
m, preferably 15 to 150 μm, more preferably 2
It is about 0 to 100 μm. The thickness of the setting retarder layer (3) may be any thickness as long as a retarding effect is exhibited for the hardening of cement, and for example, 1 to 300 μm (for example, 5 to 2).
00 μm), preferably 2-150 μm (for example, 5 μm)
120 μm), more preferably about 5 to 100 μm (for example, 10 to 100 μm), and often about 5 to 70 μm.

In such a film (A3), the curing retarding layer (3) having a uniform thickness can evenly exert the curing retarding action on the cast inorganic curable composition (mortar composition etc.). In addition, even if the curing retarder layer (3) is thin, high curing retardance can be imparted. Further, there is an advantage that it can be industrially produced at low cost and can be reinforced by a base film. Further, when the peelable hardening retardation layer (3) is formed, it is possible to easily and efficiently form a pattern or a washout surface on the surface of the concrete product with high accuracy in correspondence with the peeling site of the hardening retardation layer.

[Curing retardation film (A4)] Further, in the curing retardation film (A4) of the present invention, a pressure-sensitive adhesive layer or an adhesive layer is formed on the surface of the film (A1) (A2) or (A3). Has been done. Incidentally, when the film (A1) (A2) or (A3) has adhesiveness (for example, a film (A3 in which an adhesive layer containing a curing retarder and an adhesive or an adhesive composition is formed on a substrate film The adhesive layer or the adhesive layer is not always necessary in () and the like). The pressure-sensitive adhesive layer or the adhesive layer is a film (A1) (A
It may be formed on at least one surface of 2) or (A3), and is preferably formed on the curing retardation layer (3) in the film (A3). The pressure-sensitive adhesive layer is often formed adjacent to a layer containing a curing retarding component (such as the resin or the curing retarder).

The pressure-sensitive adhesive or the adhesive may be any pressure-sensitive adhesive substance that does not impair the curing retarding action of the curing retarding film (A1) (A2) or the curing retarding layer (3). Examples of such pressure-sensitive adhesives or adhesives include rubber-based pressure-sensitive adhesives such as natural rubber and synthetic rubber (eg, neoprene, isoprene, etc.), vinyl acetate-based elastomers such as polyvinyl acetate, ethylene-vinyl acetate copolymers, etc. It may be an emulsion of a pressure-sensitive adhesive such as an acrylic elastomer such as acrylic rubber or a polyester elastomer, or may be a solvent-type pressure-sensitive adhesive. Further, water-soluble viscous substances, for example, polyvinyl alcohol, polyacrylic acid, polyacrylamide, methyl cellulose, hydroxyethyl cellulose, synthetic water-soluble polymers such as carboxymethyl cellulose, 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 adhesive is a tackifier (for example, petroleum resin,
Hydrocarbon resins such as terpene resins and dicyclopentadiene resins, rosin derivatives, etc.) may be used together.
The pressure-sensitive adhesive layer or the adhesive layer may contain an inorganic filler or the like in order to adjust the adhesive force. The thickness of the pressure-sensitive adhesive layer can be selected within a range that exhibits adhesiveness to the decorative material and does not impair the suppressing effect on the hardening of concrete, and is, for example, 0.1 to 50 μm (for example, 1 to 50 μm), preferably 1 -40 μm, more preferably 2-30 μm
It is about 2 to 25 μm in many cases.

The pressure-sensitive adhesive layer contains a curing retarding component (for example,
(Curing retarding components and curing retarders contained in the film)
Are preferably leachable. As long as the pressure-sensitive adhesive layer capable of leaching the curing retarding component can be releasably adhered or adhered to the decorative material such as stones and tiles, the surface of the film (A1) to (A3) having curing retarding ability and curing Delay layer (3)
It may be formed uniformly or non-uniformly on the top.
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.
More preferably, it is a thin layer of about 1 to 5 μm. When the pressure-sensitive adhesive layer is formed unevenly, scattered pressure-sensitive adhesive layers may be formed regardless of the thickness.

[Manufacturing Method of Film (A4) for Delaying Curing]
The non-uniform pressure-sensitive adhesive layer or the scattered pressure-sensitive adhesive layer may be, for example, a roll method such as spray coating, gravure roll coating, reverse roll coating, comma coating method, bar coating method, curtain method coating, regular or irregular. Pattern application (eg,
It can be formed by gravure printing, flexographic printing, or other coating method). In addition, when the pressure-sensitive adhesive layer is formed of a composition containing a component such as a water-soluble resin or a water-dispersible resin through which the curing retarding component can permeate or leach, the thickness of the pressure-sensitive adhesive layer may be large. The surface of the adhesive layer is
Before use, it is often covered with a releasable protective film such as release paper or paper.

When the tackiness is imparted by the tackiness agent, the front side of the decorative material such as stones and tiles is stuck to the tacky surface, and the back side of the decorative material faces upward, and the film is arranged in the form, By casting the inorganic curable composition to cure, cleaning the surface of the concrete product taken out from the mold to remove the adhesive together with the cement paste of the uncured composition,
It is possible to obtain a concrete product in which a decorative material having a cleaned surface is integrally fixed. As is clear from the above, in order to efficiently clean the surface of the decorative material, as the pressure-sensitive adhesive, a material capable of imparting an adhesive force that can temporarily fix the decorative material, or when firmly bonding the decorative material Is preferably a material that can be removed by washing.

The curing delay film (A1) to
(A4), the curing retardation layer (3) of the film (A3), and the pressure-sensitive adhesive layer or adhesive layer of the film (4) may contain various additives. Such additives include, for example, antioxidants, ultraviolet absorbers, heat stabilizers, plasticizers, antistatic agents, and the like, extenders (fillers), pigments, and the like. As the filler, various powders such as kaolin, talc, silica and alumina can be used, but fine powders such as fine slag, fly ash, calcium carbonate, barium sulfate and silica fume (extra fine powder of silica) Is often used. As the pigment, various colorants regardless of chromatic color or achromatic color, for example, zinc oxide (ZnO), zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ),
Examples thereof include white pigments such as lithopone (ZnS + BaSO ₂ ), black pigments such as carbon black, and various colored pigments such as yellow, orange, red, purple, and blue. When zinc oxide is used among these pigments, not only the hiding power is relatively large, but also the synergistic effect with the curing retarder can enhance the setting retarding action. In addition to the zinc oxide, lead oxide and copper oxide are also useful in enhancing the setting retarding effect. The amount of the additive used depends on the type of the additive,
It can be selected within a range that does not impair the curing delay property and the strength of the film. The amount of the extender used is, for example, 100 parts by weight of the curing retardation film (A1) or (A2) or the curing retardation layer (3).
5 to 3 with respect to 100 parts by weight of the adhesive layer or the adhesive layer
The amount is 00 parts by weight, preferably 10 to 200, and more preferably 20 to 100 parts by weight. The amount of the pigment used is, for example, 1 to 2 with respect to 100 parts by weight of the curing retardation film (A1) (A2) or 100 parts by weight of the curing retardation layer (3).
The amount is 00 parts by weight, preferably 5 to 100 parts by weight, more preferably 10 to 75 parts by weight.

The hardening retardation film of the present invention is a concrete product having a pattern, a figure or a wash-out surface formed on the surface thereof,
It is useful for producing concrete products that are fixed integrally with the decorative material. That is, a film is laid in a mold with the adhesive surface as the upper surface, and the surface sides of a plurality of decorative materials such as stones and tiles are arranged by adhesive on the adhesive surface to position and fix the decorative material. Then, the inorganic curable composition is placed in the mold,
It is cured by a conventional curing method such as curing. that time,
Since the film can uniformly suppress the curing on the contact surface with the inorganic curable composition, the cured molded product is taken out of the mold, and the surface side of the decorative material (contact surface side with the film) is treated with water,
By washing with pressurized water, jet stream, etc., the uncured composition adhering to the decorative material can be easily removed, and a concrete product (decorative finishing block, precast concrete board, etc.) to which the decorative material is attached can be obtained.
Since the laid film is in surface contact with the mold, has a large contact area, and has a higher strength than paper, it is possible to prevent breakage, misalignment and the like due to the placement of the inorganic curable composition. Therefore, it is not necessary to temporarily fix it to the mold with a temporary fixing means such as double-sided adhesive tape, but if necessary,
The film may be temporarily fixed to the mold by the temporary fixing means.
Further, in a gap (joint) between the arranged decorative materials and a gap (joint) between the mold and the decorative material, a joint material (for example, polyurethane or the like) for preventing adhesion of the mortar composition or the like is used. A joint bar made of flexible plastic) may be provided.

When a hardening retardation layer that can be peeled from the base film is formed, a film having a predetermined pattern or pattern obtained by cutting the hardening retardation layer and peeling it is laid in the mold, and Patterns, figures or washout surfaces can be formed that correspond to the cutting site. In addition, when the decorative material is not adhered to the adhesive surface of the film, the aggregate can be exposed by the washing-out, and a pattern or a washed-out surface can be formed.

Further, in the case of using an adhesive film or a film on which the adhesive layer is formed, a kit in which the decorative material is previously arranged or arranged in the adhesive layer without arranging the decorative material in the formwork. The film may be placed in the mold. For example, in a film having adhesiveness (for example, an adhesive film in which an adhesive layer containing a curing retarding component such as a curing retarder is formed on the surface of a base film), a plurality of decorative materials are provided on the surface of the adhesive layer. The unit tiles can be formed by adhering the tiles as the continuous or scattered in the plane direction. In many cases, a plurality of tiles are arranged adjacent to each other (continuously) or at intervals in the plane direction (for example, the vertical direction, the horizontal direction, and the vertical and horizontal directions). When such a decoration material kit film is used, it is not necessary to separately arrange the decoration material in the mold, and it is sufficient to arrange the decoration material kit film prepared in another step in the mold. The efficiency can be increased. As the decorative material, various materials, for example, natural stones such as cobblestone, black stone, and iron flat stone, stone materials such as artificial stone, ceramic materials such as tiles, metal materials, glass materials,
Wood or woven cloth can be used. The decorative material may have a flat plate shape, and the tile may be a normal tile, a mosaic tile or a split tile. When manufacturing a concrete product, if necessary, a reinforcing material such as a reinforcing bar may be arranged 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 finished concrete product such as a precast concrete plate. That is, the decorative material kit film with the back surface of the decorative material such as the tile facing up is placed in a concrete pouring formwork, and after pouring and curing concrete, it is demolded and the adhesive film is removed. In this way, the surface of the decorative material is exposed, and the surface of the decorative material is washed with water to wash away the uncured inorganic curable composition (cement etc.) that has wrapped around the surface of the decorative material. Precast concrete boards can be manufactured. That is, even if the inorganic curable composition wraps around the surface of the decorative material such as tiles, the curing retardation component of the film or the curing retardation layer can suppress the curing of the inorganic curable composition, and the non-cured (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.

Examples of the cement include 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, burnt gypsum, etc.). Self-hardening cement; lime slag cement, blast furnace cement, etc .; mixed cement) and the like. Preferred cements include, for example, gypsum, dolomite plaster and hydraulic cements. 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, pearlite, or coarse aggregate. In the case of using the hardening retardation films (A1) to (A3) to form a pattern by the aggregate exposed on the surface with cleaning, an aggregate, particularly a mortar composition containing coarse aggregate. In many cases, the surface of at least a part of the coarse aggregate is smooth in order to improve the decorative property. The paste composition and the mortar composition, if necessary,
Colorants, hardening agents, hardening accelerators such as calcium chloride, water reducing agents such as sodium naphthalene sulfonate, coagulants,
It may contain various additives such as thickeners such as carboxymethyl cellulose, methyl cellulose and polyvinyl alcohol, foaming agents, waterproofing agents such as synthetic resin emulsions, plasticizers and the like.

The retardation film of the present invention is used for producing various concrete products, for example, curtain walls, concrete panels such as wall materials, concrete blocks and the like, particularly for producing decorative finished concrete products (for example, precast concrete boards). It is useful.

[0053]

EFFECTS OF THE INVENTION When the film for retarding curing of the present invention is used, it is possible to suppress the occurrence of breakage or displacement even when the mortar composition is cast by simply disposing the film on the mold. Further, by the retarding action of the film, the hardening on the contact surface with the mortar composition can be uniformly suppressed, and the pattern and wash-out surface can be accurately formed on the surface of the concrete product, and the decorative concrete product can be obtained. Furthermore, by disposing a film on the mold and adhering or adhering the decorative material, a concrete product integrated with the decorative material can be obtained. Furthermore, by using a film having a peelable hardening retardation layer, the hardening retardation layer is cut into a predetermined pattern and peeled off, so that even a complicated pattern depending on whether or not the surface of the concrete product is washed out can be easily formed. It can be formed and the decorativeness can be improved. In addition, a decorative material kit such as a unit tile can be obtained by adhering a surface decorative material such as a tile to a film having an adhesive layer, and the surface finish of the decorative material surface can be obtained without damaging the decorative material. It can be done easily and efficiently. Therefore, the decorative material kit can be used to decorate the surface of a concrete product with a decorative material, and a decorative concrete product such as a precast concrete board can be efficiently obtained by an automated manufacturing process or the like.

[0054]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples. Example 1 100 parts by weight of styrene-butadiene rubber latex (concentration of solid content: 30% by weight) based on 100 parts by weight of a mixture having a ratio of aminotri (methylenephosphonic acid) and citric acid of 1.5: 1 (polymerization ratio). Part, 30 parts by weight of silica fume and 10 parts by weight of zinc oxide were mixed, and the resulting fluid composition was applied to a mirror-finished stainless steel plate with a thickness of 200 μm.
Then, it was cast into a m-thick film and dried at 120 ° C. for 5 minutes to obtain a 140 μm-thick film for curing retardation.

Example 2 The fluid composition obtained in Example 1 was subjected to corona discharge treatment to form a polyethylene terephthalate film (thickness: 50 μm).
m) was coated at a coating amount of 30 g / m ² and dried at 120 ° C. for 1 minute to obtain a film in which a curing retardation layer having a thickness of 35 to 100 μm was formed on a polyethylene terephthalate film.

Example 3 Polyethylene glycol (molecular weight 300) / propylene glycol / ethylene glycol / maleic anhydride = 1
/ 1/1/3 (molar ratio) as the main component, molecular weight 3000
50 parts by weight of unsaturated polyester resin, 35 parts by weight of hydroxyethyl methacrylate, and 10 parts by weight of calcium carbonate are mixed, and 0.1 parts by weight of cobalt naphthenate and 1 part by weight of t-butylperoxybenzoate are added to the obtained mixed liquid. The parts were mixed to prepare an unsaturated polyester resin composition. The obtained composition was cast on a stainless steel plate in the same manner as in Example 1, heated at 120 ° C. for 1 minute to be cured, and then peeled off from the stainless steel plate to give a curing delay of 100 to 150 μm. A film for use was obtained.

Example 4 The unsaturated polyester resin composition obtained in Example 3 was
Corona discharge treated polypropylene film (thickness 60
20 μm in thickness and heated at 110 ° C. for 1 minute and 30 seconds to obtain a film having a 19 μm thick curing retardation layer.

[Wash-out finish] The films obtained in Examples 1 to 4 were laid on the bottom surface of a mold, and a decorative mortar composition (cement / fine aggregate / seedstone = 1/1/3 (weight ratio) )) Was cast and cured by steam curing, and then demolded, and immediately after demolding, the concrete flat plate was washed out with water. In addition, in the films of Examples 2 and 4, the curing retardation layer was laid in the mold with the upper surface facing upward.

As Comparative Example 1, a curing retarder (Lugazole F: Nippon Seeker Co., Ltd.) was directly applied (thickness: 300 g / m ² ) to the bottom plate of the mold, dried and then treated in the same manner as above. Then, the mortar composition was cast and cured, and the concrete flat plate was washed out with water.

The washability of the obtained decorative concrete flat plate was evaluated according to the following criteria, and the results shown in Table 1 were obtained. Excellent: Uniform and uniform and very good wash-out finish Good: No unevenness and good wash-out finish Poor: Some unevenness and poor wash-out finish

[0061]

[Table 1] Example 5 A pressure-sensitive adhesive (vinyl acetate-based) latex was applied on the curing retardation layer of the film obtained in Example 2 in a thickness of 10 μm,
By drying at 100 ° C. for 30 seconds, a curing retardation film having an adhesive layer (thickness 2 μm) as an upper layer was obtained.

Example 6 A film for curing retardation in which an adhesive layer (thickness 3 μm) was formed by applying an acrylic pressure sensitive adhesive at 10 μm on the curing retardation layer of the film obtained in Example 4 and drying. Got

[Stone-clad concrete block] Example 5
On the surface of the pressure-sensitive adhesive layer of the film (50 cm x 50 cm) obtained in and 6, the flat stone (about 15 cm x 15 cm)
× Thickness of about 2 cm) 9 pieces were arranged and adhered to each other to prepare a decorative material kit film. Even if the film was lifted so that the stone was oriented vertically, the stone did not fall off the film. Further, instead of the flat stone material, a flat tile or a split tile was used and adhered to the surface of the adhesive layer of the film in the same manner as above. Each of the above films with stone, flat tile, and split tile adhered to the mold (50 cm x 50 c
(m × 10 cm) laid on a bottom plate, and then cast a mortar composition (water 0.5 / cement 1 / sand 2 (weight ratio)),
It was cured by steaming for 1 day. Two days after the demolding, the mortar adhering to the surface of the stone or tile of the concrete product and the mortar uncured portion between joints were washed away with high pressure water.

As Comparative Example 2, an acrylic pressure sensitive adhesive was applied to a corona discharge treated polypropylene film (thickness 60 μm) at a thickness of 10 μm without forming a curing retardation layer, and dried to form a pressure sensitive adhesive layer (thickness 3 μm). ) Was used. That is, instead of the films of Examples 1 and 2, except that a film in which only an adhesive layer is formed is used, stone materials, flat tiles and split tiles are adhered in the same manner as described above, and the mortar composition is cast. Then, the mortar adhered to the surface of the stone or tile and the uncured portion of the mortar between the joints were washed away with high pressure water. The surface condition of the obtained stone-clad concrete block was observed, and the ratio of the perimeter of the mortar attached to the stone or tile to the total perimeter of the stone or tile was calculated, and the results shown in Table 2 were obtained. .

[0065]

[Table 2] By using the films obtained in Examples 5 and 6, it was possible to obtain a beautiful stone-clad concrete block in which stones and tiles were exposed on the surface.

Comparative Example 3 One side of a polyethylene terephthalate film having a thickness of 50 μm was subjected to corona discharge treatment, and then an acrylic adhesive was applied to the corona discharge treated surface in a gravure roll system at 39 g / m ² in terms of solid content, By drying, an adhesive sheet having an adhesive layer formed was obtained.

Comparative Example 4 The coating amount of acrylic pressure-sensitive adhesive was 247 g / m in terms of solid content.
An adhesive sheet was obtained in the same manner as in Comparative Example 3 except that the number was changed to ² .

Example 7 A pressure-sensitive adhesive composition composed of 72% by weight of acrylic pressure-sensitive adhesive (solid content) and 28% by weight of concrete hardening retarder composition was used except that the coating amount was 217 g / m ^{2 in} terms of solid content. A pressure-sensitive adhesive sheet was obtained in the same manner as in Comparative Example 3. The concrete hardening retarder composition is polyethylene glycol / propylene glycol / ethylene glycol /
0.1 parts by weight of cobalt naphthenate was added to a mixed solution of 50 parts by weight of unsaturated polyester resin having a weight average molecular weight of 3000, obtained by using maleic anhydride as a main reaction component, 35 parts by weight of hydroxyethyl methacrylate, and 10 parts by weight of calcium carbonate. And t-butyl peroxybenzoate (1 part by weight).

Example 8 A pressure-sensitive adhesive sheet was obtained in the same manner as in Comparative Example 3 except that the coating amount of the pressure-sensitive adhesive composition prepared in Example 7 was 246 g / m ^{2 in} terms of solid content.

Example 9 A pressure-sensitive adhesive sheet was obtained in the same manner as in Comparative Example 3 except that the coating amount of the pressure-sensitive adhesive composition prepared in Example 7 was 100 g / m ^{2 in} terms of solid content.

Example 10 52% by weight of acrylic adhesive (solid content) and Example 3
A pressure-sensitive adhesive sheet was obtained in the same manner as in Comparative Example 3 except that the coating amount of the pressure-sensitive adhesive composition composed of 48% by weight of the concrete hardening retarder composition of was 50 g / m ^{2 in} terms of solid content. Example 11 A pressure-sensitive adhesive sheet was obtained in the same manner as in Comparative Example 3 except that the coating amount of the pressure-sensitive adhesive composition prepared in Example 10 was 110 g / m ^{2 in} terms of solid content.

Example 12 A pressure-sensitive adhesive sheet was obtained in the same manner as in Comparative Example 3 except that the coating amount of the pressure-sensitive adhesive composition prepared in Example 10 was 200 g / m ^{2 in} terms of solid content.

Then, the surface of the tile (about 15 cm × 15 cm) was brought into contact with the surface of the adhesive layer of the pressure-sensitive adhesive sheets (50 cm × 50 cm) obtained in Comparative Examples 3 to 4 and Examples 7 to 12, and the length and width were adjusted. 3 tiles in each direction (9 total)
Were arranged in a planar direction and attached to prepare a unit tile. Form the unit tile for concrete pouring (50c
(m × 50 cm × 50 cm), the concrete was poured into the bottom for curing, the mold was removed, the adhesive sheet was removed, and the exposed surface of the tile was washed with water to obtain a precast concrete plate.

On the precast concrete boards obtained by using the pressure-sensitive adhesive sheets of Comparative Examples 3 and 4, the cement that had wrapped around the surface of the tile was hardened and firmly adhered,
In order to remove the hardened cement that could not be removed by washing with water, a mechanical surface finishing process was required. On the other hand, in the precast concrete boards obtained by using the pressure-sensitive adhesive sheets of Examples 7 to 12, the cement wrapping around the surface of the tile was not completely cured even after the curing was completed,
The cement adhering to the tile surface could be removed simply by washing with water, and the surface could be easily finished while preventing damage to the tile.

The adhesiveness between the adhesive layer and the tile in the unit tiles obtained by using the adhesive sheets of Comparative Examples 3 and 4 and Examples 7 to 12 (that is, the holding property of the adhesive layer with respect to the tile) is All were good.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication location C09J 7/02 JHR C09J 7/02 JHR JKK JKK JLE JLE JLJ JLJ E04F 13/02 8913-2E E04F 13 / 02 F 13/08 102 8913-2E 13/08 102U (72) Inventor Takaaki Murai 8-3-2 Kuba, Otake City, Hiroshima Prefecture (72) Inventor Kiyoshi Okitsu 5-29, Kotobukicho, Shizuoka City (72) Inventor Yoshiyuki Ikemoto 1716-1, Homukai-cho, Hodogaya-ku, Yokohama, Kanagawa (72) Inventor Hisayuki Matsuo 1-8-3 Shimbashi, Minato-ku, Tokyo Inside Nippon Concrete Industrial Co., Ltd. (72) Takehiko Maruyama Ibaraki Shimodate 218-3 Kitajuku, Isayama-shi, Japan Inside the Research Institute of Japan Concrete Industry Co., Ltd. (72) Inventor Shigeno Sekine 52 Kanto, Fujinomiya-shi, Shizuoka No. 7 Co., Ltd.

Claims (26)

[Claims] 1. A film for retarding cement hardening, which has an ability of retarding hardening of cement and has tackiness or adhesiveness. 2. The film for retarding cement hardening according to claim 1, wherein the film is composed of a resin (1) having a cement hardening retarding ability. 3. The film comprises a cement hardening retarder (2).
The film for retarding cement hardening according to claim 1, comprising: 4. The cement hardening retardation film according to claim 3, wherein the hardening retarder (2) is contained in an amount of 2 to 1000 parts by weight based on 100 parts by weight of the resin capable of forming a film. 5. A resin (1) having a cement hardening retarding ability.
The film for retarding cement hardening according to claim 2 or 3, wherein the film composed of or the film containing the cement hardening retarder (2) contains an adhesive or an adhesive. 6. A resin (1) or a cement hardening retarder (2) having a cement hardening retarding ability on the surface of a substrate film.
The film for delaying hardening of cement according to claim 1, wherein a hardening delay layer containing is formed, and the base film or the hardening delay layer has tackiness or adhesiveness. 7. The cement hardening retardation film according to claim 6, wherein the hardening retardation layer is peelable from the substrate film. 8. A resin (1) having a cement hardening retarding ability.
The film for retarding cement hardening according to claim 2, 5 or 6, wherein is an unsaturated polyester resin. 9. The curing retarder is a phosphonic acid compound, an oxycarboxylic acid, a polyvalent carboxylic acid, a homo- or copolymer of a monomer having a carboxyl group, isoalcorbic acid,
The film for retarding cement hardening according to any one of claims 3 to 6, which is at least one component selected from the group consisting of phosphoric acid, boric acid or salts thereof, polyhydroxysilane, and hexafluorosilicate. . 10. The cement hardening retardation film according to claim 6, wherein the hardening retardation layer has tackiness or adhesiveness. 11. The cement hardening retardation film according to claim 1, wherein a pressure-sensitive adhesive layer or an adhesive layer is formed on the surface of the film. 12. The cement hardening retardation film according to claim 6, 7 or 10, wherein an adhesive layer or an adhesive layer is formed on the hardening retardation layer. 13. The cement hardening retardation film according to claim 11, wherein the hardening retarding component can be leached into the pressure-sensitive adhesive layer or the adhesive layer. 14. The adhesive layer or the adhesive layer has a thickness of 0.1.
The film for retarding cement hardening according to claim 13, which has a thickness of -50 μm. 15. The cement hardening retardation film according to claim 13 or 14, wherein the pressure-sensitive adhesive layer or the adhesive layer is formed scattered on the hardening retardation layer. 16. The film for retarding cement hardening according to claim 11, wherein the pressure-sensitive adhesive layer or the adhesive layer is composed of a water-soluble or water-dispersible resin. 17. A method for producing a film for retarding cement hardening, which comprises film-forming a resin composition containing a resin (1) having a cement hardening retarding ability and an adhesive or an adhesive. 18. A method for producing a film for retarding cement hardening, which comprises film-molding a resin composition comprising a cement hardening retarder (2) and an adhesive or an adhesive. 19. The method for producing a film for retarding cement hardening according to claim 17, wherein the film is formed by a casting method. 20. A cement setting retarder for forming a setting retardation layer containing a resin (1) or a cement setting retarder (2) having a cement setting retarding ability and an adhesive or an adhesive on the surface of a base film. Film manufacturing method. 21. The method for producing a film for retarding cement hardening according to claim 17, 18 or 20, wherein a pressure-sensitive adhesive layer or an adhesive layer is formed on the surface of the film. 22. A coating liquid containing a resin (1) having a cement hardening retarding ability or a cement hardening retarder (2) is applied to the surface of a substrate film, and an adhesive layer or a pressure-sensitive adhesive layer is formed on the formed hardening retardation layer. A method for producing a film for retarding cement hardening, which comprises forming an adhesive layer. 23. A thin pressure-sensitive adhesive layer or adhesive layer capable of leaching a curing retarding component is formed on the curing retarding layer.
3. The method for producing a film for retarding cement hardening according to 2. 24. The film for delaying hardening of cement according to claim 20, wherein a coating solution is applied to a base film having a surface tension of 38 dyn / cm or less to form a set retardation layer which can be peeled from the base film. Manufacturing method. 25. The sticky or adhesive property of claim 1,
A decorative material kit film in which a plurality of decorative materials are adhered to the adhesive surface or the adhesive surface of 5, 10, 11 or 12 in a continuous or scattered manner. 26. The decorative material kit film according to claim 25 is placed in a mold, and after the inorganic curable composition is cast and cured, the film is released from the mold to give a tacky or adhesive film. A method for producing a decorative concrete product, which comprises removing and cleaning the surface of an exposed decorative material.