WO2015178353A1 - Film stratifié pour former une couche de revêtement d'une surface en béton, matériau de construction en béton et son procédé de production - Google Patents

Film stratifié pour former une couche de revêtement d'une surface en béton, matériau de construction en béton et son procédé de production Download PDF

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WO2015178353A1
WO2015178353A1 PCT/JP2015/064230 JP2015064230W WO2015178353A1 WO 2015178353 A1 WO2015178353 A1 WO 2015178353A1 JP 2015064230 W JP2015064230 W JP 2015064230W WO 2015178353 A1 WO2015178353 A1 WO 2015178353A1
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concrete
resin composition
curable resin
meth
film
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PCT/JP2015/064230
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English (en)
Japanese (ja)
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寛幸 中島
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日本合成化学工業株式会社
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Priority claimed from JP2015042320A external-priority patent/JP6565222B2/ja
Application filed by 日本合成化学工業株式会社 filed Critical 日本合成化学工業株式会社
Priority to CN201580025922.0A priority Critical patent/CN106458774B/zh
Priority to EP15795752.3A priority patent/EP3147271B1/fr
Publication of WO2015178353A1 publication Critical patent/WO2015178353A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
    • C04B41/62—Coating or impregnation with organic materials
    • C04B41/63—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
    • C04B41/70—Coating or impregnation for obtaining at least two superposed coatings having different compositions
    • C04B41/71—Coating or impregnation for obtaining at least two superposed coatings having different compositions at least one coating being an organic material

Definitions

  • the present invention relates to a laminated film for forming a concrete surface covering layer, a concrete building material, and a method for producing the same. More specifically, the present invention is for forming a concrete surface coating layer excellent in protective properties for protecting the concrete surface from scratches and surface smoothness for smoothing the concrete surface and improving design properties.
  • the present invention relates to a laminated film, and also relates to a concrete building material produced using the laminated film of the present invention and a method for producing the same.
  • the surface of concrete such as lightweight cellular concrete (ALC) is painted to protect the base material, prevent performance degradation due to water intrusion, and neutralize due to carbon dioxide intrusion.
  • ALC lightweight cellular concrete
  • lightweight cellular concrete is usually boarded in a manufacturing plant and brought to a construction site, and this is laid on a framework to form a building, and then the outer wall surface is painted. is there.
  • Such lightweight cellular concrete board has a foamed structure, so damage such as chipping is likely to occur during transportation. Also, during transportation and construction, dust from fine cracks and chips, etc., drops due to the foamed structure.
  • a coating method is often employed.
  • coating materials repeatedly such as “undercoating”, “intermediate coating”, and “overcoating”, and these coating materials are often dispersed or diluted in a liquid.
  • the liquid component is often dried repeatedly.
  • the liquid component forming the coating material is an organic solvent
  • a method of replacing the liquid component with water by using an emulsification technique is now quite popular.
  • thermosetting resin powder mixed with siliceous raw material powder is applied to the concrete surface, and the thermosetting resin powder is cured by autoclave curing.
  • a method and the like have also been proposed (see, for example, Patent Document 1).
  • Patent Document 1 it is necessary to apply the coating layer by electrostatic spray or the like when forming the coating layer on the concrete surface, which is inferior in productivity and workability. Furthermore, further improvements have been demanded in terms of the protection of the concrete surface and the surface smoothness for smoothing the concrete surface and improving the design.
  • the productivity and workability are excellent, the permeability to concrete (adhesion with concrete) is good, and the concrete surface is protected and has a smooth surface.
  • the object is to form an excellent coating layer on the concrete surface.
  • the inventor of the present invention when forming a coating layer on the concrete surface using the curable resin composition, the lamination of the layer made of the curable resin composition and the support film By sticking the film to the concrete surface and curing the curable resin composition layer, it has excellent productivity and workability, good permeability to concrete (adhesion with concrete), and the concrete surface It was found that a coating layer having excellent protective properties and surface smoothness was formed, and the present invention was completed.
  • the gist of the present invention is as follows ⁇ 1> to ⁇ 16>.
  • ⁇ 1> A laminated film for forming a concrete surface coating layer, wherein a layer comprising a curable resin composition and a support film are laminated.
  • ⁇ 2> The laminated film for forming a concrete surface coating layer according to ⁇ 1>, wherein the curable resin composition is a curable resin composition containing a compound having an unsaturated group.
  • the curable resin composition comprises a binder polymer (A), a reactive oligomer (B) having one or more unsaturated groups, a reactive monomer (C) having one or more unsaturated groups, and a polymerization initiator (
  • ⁇ 5> The concrete surface coating layer according to the above ⁇ 3> or ⁇ 4>, wherein the reactive oligomer (B) having one or more unsaturated groups is a urethane (meth) acrylate compound (b1). A laminated film for forming.
  • ⁇ 6> The concrete according to any one of the above ⁇ 3> to ⁇ 5>, wherein the reactive monomer (C) having one or more unsaturated groups is a polyfunctional (meth) acrylate compound (c1). A laminated film for forming a surface coating layer.
  • ⁇ 10> The laminated film for forming a concrete surface coating layer according to any one of the above ⁇ 1> to ⁇ 9>, wherein the layer made of the curable resin composition has a thickness of 50 ⁇ m or more.
  • ⁇ 11> a support film, a layer composed of the curable resin composition described in the above ⁇ 8> or ⁇ 9>, and a layer composed of the curable resin composition described in any one of the above ⁇ 1> to ⁇ 7>.
  • ⁇ 12> The laminated film for forming a concrete surface covering layer according to any one of the above ⁇ 1> to ⁇ 11>, wherein a protective film is laminated on the opposite side to the support film in the thickness direction.
  • ⁇ 13> The laminated film for forming a concrete surface coating layer according to any one of ⁇ 1> to ⁇ 12>, wherein the concrete is lightweight cellular concrete.
  • ⁇ 14> Concrete, and a concrete surface coating layer formed by curing a layer made of the curable resin composition according to any one of ⁇ 1> to ⁇ 13>, and covering a surface of the concrete. Concrete building material.
  • ⁇ 15> The concrete building material according to ⁇ 14>, wherein the concrete is lightweight cellular concrete.
  • ⁇ 16> A method for producing the concrete building material according to ⁇ 14> or ⁇ 15> above, Bonding the concrete film for forming a concrete surface coating layer according to any one of the above ⁇ 1> to ⁇ 13> to the concrete so that the layer made of the curable resin composition is in contact with the surface of the concrete; And a step of curing a layer made of the curable resin composition to form a concrete surface covering layer on the surface of the concrete.
  • the laminated film for forming a concrete surface coating layer of the present invention is excellent in productivity and workability in forming a coating layer on the concrete surface, has good permeability to concrete (adhesion with concrete), It has the effect of being excellent in the protection and smoothness of the concrete surface.
  • FIG. 1 is a cross-sectional view schematically showing an example of a laminated film for forming a concrete surface coating layer of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing another example of the laminated film for forming a concrete surface coating layer of the present invention.
  • FIG. 3 is a cross-sectional view schematically showing a process of forming a coating layer on the concrete surface using the laminated film for forming a concrete surface coating layer of the present invention shown in FIG.
  • the laminated film for forming a concrete surface coating layer of the present invention is characterized in that a layer made of a curable resin composition and a support film are laminated.
  • the curable resin composition will be described.
  • the curable resin composition used in the present invention is a resin composition that can be cured by heat and / or active energy rays, and is preferably a thermosetting resin composition in terms of imparting higher weather resistance. .
  • a curable resin composition is preferably a curable resin composition containing a compound having an unsaturated group.
  • the compound having an unsaturated group include reactive oligomers and reactive monomers having one or more unsaturated groups.
  • the curable resin composition is preferably a binder polymer (A), a reactive oligomer (B) having one or more unsaturated groups, a reactive monomer (C) having one or more unsaturated groups, and a polymerization initiator. (D) is contained.
  • A binder polymer
  • B reactive oligomer
  • C reactive monomer having one or more unsaturated groups
  • D polymerization initiator
  • the binder polymer (A) in the present invention is used for the purposes of moderate flexibility of the uncured film and suppression of surface tackiness, improvement of the durability of the cured film and adjustment of the hardness, for example, (meth) acrylic Resins, polyurethane resins, epoxy resins and the like can be mentioned.
  • (meth) acrylic resin (a1) is preferable in terms of facilitating adjustment of durability and hardness of the cured film.
  • the (meth) acrylic resin (a1) will be described more specifically.
  • (meth) acryl represents acryl or methacryl
  • (meth) acrylate represents acrylate or methacrylate.
  • the (meth) acrylic resin (a1) in the present invention is obtained by polymerizing a monomer component containing a (meth) acrylic monomer.
  • (Meth) acrylic-type resin (a1) can be used individually by 1 type or in combination of 2 or more types.
  • the (meth) acrylic resin (a1) preferably contains the (meth) acrylic acid ester monomer (a2) as the main polymerization component, and if necessary, the functional group-containing monomer (a3) and other copolymers.
  • the polymerizable monomer (a4) can also be used as a copolymerization component.
  • the (meth) acrylic acid ester monomer (a2) include, for example, aliphatic (meth) acrylic acid ester monomers such as (meth) acrylic acid alkyl ester, and aromatic monomers such as (meth) acrylic acid phenyl ester. Examples include (meth) acrylic acid ester monomers.
  • the alkyl group usually has 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 4 to 8 carbon atoms, and specifically, methyl (meth) acrylate.
  • Examples of the (meth) acrylic acid phenyl ester include benzyl (meth) acrylate and phenoxyethyl (meth) acrylate.
  • Examples of other (meth) acrylic acid ester monomers (a2) include tetrahydrofurfuryl (meth) acrylate. These can be used alone or in combination of two or more.
  • (meth) acrylic acid ester monomers (a2) methyl (meth) acrylate, n-butyl (meth) acrylate, 2) in terms of copolymerizability, adhesive physical properties, ease of handling, and availability of raw materials.
  • -Ethylhexyl (meth) acrylate is preferably used.
  • Examples of the functional group-containing monomer (a3) include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an alkoxy group-containing monomer, a phenoxy group-containing monomer, an amide group-containing monomer, an amino group-containing monomer, other nitrogen-containing monomers, and a glycidyl group-containing Monomers, phosphoric acid group-containing monomers, sulfonic acid group-containing monomers and the like can be mentioned, and these can be used alone or in combination of two or more.
  • Examples of the hydroxyl group-containing monomer include a primary hydroxyl group-containing monomer, a secondary hydroxyl group-containing monomer, and a tertiary hydroxyl group-containing monomer.
  • Examples of the primary hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyoctyl.
  • (Meth) acrylic acid hydroxyalkyl ester containing primary hydroxyl group such as (meth) acrylate, 10-hydroxydecyl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate; caprolactone-modified 2-hydroxyethyl
  • Caprolactone-modified monomers such as (meth) acrylate; 2-acryloyloxyethyl-2-hydroxyethylphthalic acid; N-methylol (meth) acrylamide; N-hydroxyethyl (meth) acrylamide It is.
  • Examples of the secondary hydroxyl group-containing monomer include secondary hydroxyl group-containing (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate; 2-hydroxy-3-phenoxy And propyl (meth) acrylate; 3-chloro-2-hydroxypropyl (meth) acrylate; 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like.
  • Examples of the tertiary hydroxyl group-containing monomer include 2,2-dimethyl-2-hydroxyethyl (meth) acrylate and the like.
  • hydroxyl group-containing monomer examples include polyethylene glycol derivatives such as diethylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate, polypropylene glycol derivatives such as polypropylene glycol mono (meth) acrylate, and polyethylene glycol-polypropylene glycol-mono (meta).
  • Oxyalkylene-modified monomers such as acrylate, poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate may be used.
  • carboxyl group-containing monomer examples include Michael addition of acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, acrylamide N-glycolic acid, cinnamic acid, and (meth) acrylic acid.
  • 2- (meth) acryloyloxyethyl dicarboxylic acid monoester for example, 2-acryloyloxyethyl) Succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxyethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexa Dorofutaru acid monoester, 2-methacryloyloxyethyl hexahydrophthalic acid mono ester) and the like.
  • Such a carboxyl group-containing monomer may be used as an acid, or may be used in the form of a salt neutralized with an alkali.
  • alkoxy group-containing monomer examples include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, and 2-butoxydiethylene glycol.
  • (Meth) acrylate methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, octoxypolyethylene glycol Polypropylene glycol mono (meth) acrylate, Lauroxy polyethylene glycol mono (meth) acrylate, Examples include aliphatic (meth) acrylic acid esters such as loxypolyethylene glycol mono (meth) acrylate.
  • phenoxy group-containing monomer examples include 2-phenoxyethyl (meth) acrylate and phenoxypolyethylene glycol (meth) acrylate.
  • acrylate esters of aromatic (meth) acrylates such as phenoxypolyethylene glycol-polypropylene glycol (meth) acrylate and nonylphenol ethylene oxide adduct (meth) acrylate.
  • Examples of the amide group-containing monomer include acrylamide, methacrylamide, N- (n-butoxyalkyl) acrylamide, N- (n-butoxyalkyl) methacrylamide, N, N-dimethyl (meth) acrylamide, N, N- Examples include diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, acrylamide-3-methylbutylmethylamine, dimethylaminoalkylacrylamide, and dimethylaminoalkylmethacrylamide.
  • amino group-containing monomer examples include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and a quaternized product thereof.
  • nitrogen-containing monomer other than the amide group-containing monomer and the amino group-containing monomer examples include acryloylmorpholine.
  • Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate and allyl glycidyl ether.
  • Examples of the phosphoric acid group-containing monomer include 2- (meth) acryloyloxyethyl acid phosphate, bis (2- (meth) acryloyloxyethyl) acid phosphate, and the like.
  • sulfonic acid group-containing monomer examples include olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid, and methallyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, styrene sulfonic acid, and salts thereof. .
  • Examples of other copolymerizable monomer (a4) include acrylonitrile, methacrylonitrile, styrene, ⁇ -methylstyrene, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, Examples thereof include vinyl pyridine, vinyl pyrrolidone, itaconic acid dialkyl ester, fumaric acid dialkyl ester, allyl alcohol, acrylic chloride, methyl vinyl ketone, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, and dimethylallyl vinylketone.
  • ethylene glycol di (meth) acrylate For the purpose of increasing the molecular weight, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate
  • a compound having two or more ethylenically unsaturated groups such as divinylbenzene can also be used in combination.
  • the content ratio of the (meth) acrylic acid ester monomer (a2), the functional group-containing monomer (a3), and the other copolymerizable monomer (a4) is (meth) acrylic acid.
  • the ester monomer (a2) is preferably 10 to 100% by weight, particularly preferably 20 to 95% by weight
  • the functional group-containing monomer (a3) is preferably 0 to 90% by weight, particularly preferably 5 to 80% by weight.
  • the other copolymerizable monomer (a4) is preferably 0 to 50% by weight, particularly preferably 5 to 40% by weight.
  • the (meth) acrylic resin (a1) in the present invention is completed in that it is excellent in compatibility with a urethane (meth) acrylate compound suitable as a reactive oligomer (B) having one or more unsaturated groups.
  • a polymer having methyl (meth) acrylate as a polymerization component particularly preferably a polymer having methyl methacrylate as a polymerization component, Is preferably polymethyl methacrylate.
  • the (meth) acrylic resin (a1) can be produced by polymerizing the monomer components (a2) to (a4).
  • Such polymerization can be performed by a conventionally known method such as solution radical polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization.
  • a polymerization monomer such as the (meth) acrylic acid ester monomer (a2), a functional group-containing monomer (a3), other copolymerizable monomer (a4), a polymerization initiator (azobisisobutyrate) Ronitrile, azobisisovaleronitrile, benzoyl peroxide, etc.
  • azobisisobutyrate Ronitrile, azobisisovaleronitrile, benzoyl peroxide, etc.
  • organic solvent used in the polymerization reaction examples include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, esters such as ethyl acetate and butyl acetate, n-propyl alcohol, and isopropyl alcohol.
  • aromatic hydrocarbons such as toluene and xylene
  • aliphatic hydrocarbons such as hexane
  • esters such as ethyl acetate and butyl acetate
  • n-propyl alcohol and isopropyl alcohol.
  • Aliphatic alcohols such as acetone, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
  • the glass transition temperature (Tg) of the (meth) acrylic resin (a1) is usually 40 to 120 ° C., preferably 60 to 110 ° C. If the glass transition temperature is too high, the amount of the (meth) acrylic resin (a1) that can be blended when preparing the curable resin composition is limited, and the adjustment range of durability and flexibility of the coating layer is narrowed. As a result, the durability of the coating layer tends to decrease, or the strength tends to decrease because the coating layer becomes too hard. If the glass transition temperature is too low, the thermal durability of the coating layer tends to decrease.
  • the weight average molecular weight of the (meth) acrylic resin (a1) thus obtained is usually 10,000 to 3,000,000, preferably 20,000 to 2.5 million.
  • the weight average molecular weight is too small, the uncured curable resin composition becomes soft, and the tackiness is unnecessarily high, and the handling property tends to be lowered. Further, the cured curable resin composition Tend to be brittle.
  • the viscosity of the curable resin composition before coating tends to be too high, or the coating property tends to decrease, such as difficulty in increasing the concentration. Furthermore, there exists a tendency that the softness
  • said weight average molecular weight is based on standard polystyrene molecular weight conversion, column: Shodex GPC KF in high performance liquid chromatography (The product of Japan Waters, "Waters2695 (main body)” and “Waters2414 (detector)”).
  • -806L exclusion limit molecular weight: 2 ⁇ 10 7 , separation range: 100 to 2 ⁇ 10 7 , theoretical plate number: 10,000 plates / piece, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 ⁇ m
  • Reactive oligomer (B) having one or more unsaturated groups examples include urethane (meth) acrylate compounds (b1), epoxy (meth) acrylate compounds, polyester (meth) acrylate compounds, and the like. Can be mentioned. Among these, the urethane (meth) acrylate compound (b1) is preferable from the viewpoint of imparting appropriate elasticity to the cured film. Hereinafter, the urethane (meth) acrylate compound (b1) will be described more specifically.
  • the urethane (meth) acrylate compound (b1) used in the present invention is obtained by reacting a hydroxyl group-containing (meth) acrylate compound (b2), a polyvalent isocyanate compound (b3), and a polyol compound (b4).
  • a urethane (meth) acrylate type compound (b1) is mentioned.
  • the weight average molecular weight of the urethane (meth) acrylate compound (b1) used in the present invention is preferably 500 to 50000, more preferably 1000 to 30000. If the weight average molecular weight is too small, the coating layer tends to become brittle, and if it is too large, the coating layer becomes too hard and impact resistance tends to decrease.
  • the above-mentioned weight average molecular weight is a weight average molecular weight in terms of standard polystyrene molecular weight, and the column: Shodex GPC KF-806L (excluding Limit molecular weight: 2 ⁇ 10 7 , separation range: 100 to 2 ⁇ 10 7 , theoretical plate number: 10,000 plate / piece, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 ⁇ m) It can be measured by using a series.
  • the urethane (meth) acrylate compound (b1) has a viscosity at 60 ° C. of preferably 500 to 150,000 mPa ⁇ s, particularly preferably 500 to 120,000 mPa ⁇ s, and still more preferably 1,000 to 100,000 mPa ⁇ s. -S.
  • the viscosity can be measured with an E-type viscometer.
  • hydroxyl group-containing (meth) acrylate compound (b2) examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth).
  • hydroxyalkyl (meth) acrylates such as 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethyl acryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth) ) Acrylate, dipropylene glycol (meth) acrylate, fatty acid modified-glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyl-oxypropyl methacrylate, pentaerythritol tri (meth) acrylate, caprolactone-modified penta Erythritol tri (meth) acrylate
  • a hydroxyl group (meth) acrylate compound having one ethylenically unsaturated group is preferred for the reason that it can reduce curing shrinkage during the formation of a coating layer, and 2-hydroxyethyl (meth) is particularly preferred.
  • Hydroxyalkyl (meth) acrylates such as acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and It is preferable to use 2-hydroxyethyl (meth) acrylate in terms of excellent reactivity and versatility. Moreover, these can be used individually by 1 type or in combination of 2 or more types.
  • polyisocyanate compound (b3) examples include aromatics such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate.
  • Aliphatic polyisocyanates such as polyisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (Isocyanatomethyl) Cycloaliphatic polyisocyanates such as hexane, trimer compounds or multimeric compounds of these polyisocyanates, allophanate type polyisocyanates, burette type polyisocyanates, water-dispersed polyisocyanates (for example, manufactured by Nippon Polyurethane Industry Co., Ltd.) "Aquanate 100", “Aquanate 110", “Aquanate 200", “Aquanate 210", etc.).
  • aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,
  • An alicyclic diisocyanate such as 3-bis (isocyanatomethyl) cyclohexane is preferably used, and isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate is particularly preferably used in terms of low curing shrinkage, and Preferably, isophorone diisocyanate is used in terms of excellent reactivity and versatility.
  • polyol compound (b4) examples include polyether glycol, polyester polyol, polycarbonate polyol, polyolefin polyol, polybutadiene polyol, (meth) acrylic polyol, polysiloxane polyol, and the like. And alkylene glycols such as propylene glycol and neopentyl glycol.
  • polyether polyol examples include, for example, polyether glycols containing an alkylene structure such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, and polyhexamethylene glycol, and random or block copolymers of these polyalkylene glycols. Examples include coalescence.
  • polyester-based polyol examples include three types of components: a condensation polymer of a polyhydric alcohol and a polycarboxylic acid; a ring-opening polymer of a cyclic ester (lactone); a polyhydric alcohol, a polycarboxylic acid, and a cyclic ester. And the like.
  • polyhydric alcohol examples include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, 2-methyl-1,3-trimethyl.
  • Methylene diol 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl-1,5-pentamethylene diol, glycerin , Trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), sugar alcohols (such as xylitol and sorbitol)
  • polyvalent carboxylic acid examples include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; -Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, trimellitic acid, and the like.
  • aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid
  • -Alicyclic dicarboxylic acids such as
  • cyclic ester examples include propiolactone, ⁇ -methyl- ⁇ -valerolactone, and ⁇ -caprolactone.
  • polycarbonate polyol examples include a reaction product of a polyhydric alcohol and phosgene; a ring-opening polymer of a cyclic carbonate (such as alkylene carbonate).
  • polyhydric alcohol examples include polyhydric alcohols exemplified in the description of the polyester-based polyol, and examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, and the like. It is done.
  • the polycarbonate polyol may be a compound having a carbonate bond in the molecule and having a terminal hydroxyl group, and may have an ester bond together with the carbonate bond.
  • polyolefin-based polyol examples include those having a saturated hydrocarbon skeleton having a homopolymer or copolymer such as ethylene, propylene and butene, and having a hydroxyl group at the molecular end.
  • polybutadiene-based polyol examples include those having a butadiene copolymer as a hydrocarbon skeleton and having a hydroxyl group at the molecular end.
  • the polybutadiene-based polyol may be a hydrogenated polybutadiene polyol in which all or part of the ethylenically unsaturated groups contained in the structure thereof are hydrogenated.
  • Examples of the (meth) acrylic polyol include those having at least two hydroxyl groups in the molecule of the polymer or copolymer of the (meth) acrylic acid ester.
  • polysiloxane polyol examples include dimethyl polysiloxane polyol and methylphenyl polysiloxane polyol.
  • polyester-based polyols and polyether-based polyols are preferable, and polyester-based polyols are particularly preferable because they are excellent in mechanical properties such as flexibility during curing.
  • the weight-average molecular weight of the polyol compound (b4) is preferably 500 to 8000, particularly preferably 550 to 5000, and more preferably 600 to 3000. If the molecular weight of the polyol compound (b4) is too large, mechanical properties such as coating film hardness tend to decrease during curing, and if too small, curing shrinkage tends to increase and stability tends to decrease.
  • the above-mentioned weight average molecular weight is a weight average molecular weight in terms of standard polystyrene molecular weight, and the column: Shodex GPC KF-806L (excluding Limit molecular weight: 2 ⁇ 10 7 , separation range: 100 to 2 ⁇ 10 7 , theoretical plate number: 10,000 plate / piece, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 ⁇ m) It can be measured by using a series.
  • the urethane (meth) acrylate compound (b1) is usually the above-mentioned hydroxyl group-containing (meth) acrylate compound (b2), polyvalent isocyanate compound (b3) and polyol compound (b4) in a reactor or separately. It can be manufactured by charging and reacting. Further, the reaction product obtained by reacting the polyol compound (b4) and the polyvalent isocyanate compound (b3) in advance is reacted with the hydroxyl group-containing (meth) acrylate compound (b2) to obtain urethane (meth) acrylate.
  • the compound (b1) can also be produced, and this production method is useful in terms of reaction stability, reduction of byproducts, and the like.
  • the reaction between the polyol compound (b4) and the polyvalent isocyanate compound (b3) known reaction means can be used.
  • the molar ratio of the isocyanate group in the polyvalent isocyanate compound (b3) to the hydroxyl group in the polyol compound (b4) is usually about 2n: (2n-2) (n is an integer of 2 or more).
  • the addition reaction of the reaction product obtained by reacting the polyol compound (b4) and the polyvalent isocyanate compound (b3) in advance with the hydroxyl group-containing (meth) acrylate compound (b2) is also a known reaction. Means can be used.
  • the reaction molar ratio between the reaction product and the hydroxyl group-containing (meth) acrylate compound (b2) is, for example, that the polyisocyanate compound (b3) has two isocyanate groups and the hydroxyl group-containing (meth) acrylate compound (b2).
  • ) Has one hydroxyl group, the reaction product: hydroxyl group-containing (meth) acrylate compound (b2) is about 1: 2, and the polyisocyanate compound (b3) has three isocyanate groups.
  • the reaction product: hydroxyl group-containing (meth) acrylate compound (b2) is about 1: 3.
  • a catalyst is used for the purpose of promoting the reaction. It is also preferable to use.
  • organometallic compounds such as dibutyltin dilaurate, trimethyltin hydroxide, tetra-n-butyltin, zinc octoate, tin octoate, cobalt naphthenate, stannous chloride, stannic chloride and the like.
  • Metal salts triethylamine, benzyldiethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undecene, N, N, N ′, N′-tetramethyl-
  • amine-based catalysts such as 1,3-butanediamine and N-ethylmorpholine, bismuth nitrate, bismuth bromide, bismuth iodide, bismuth sulfide and the like, organic bismuth compounds such as dibutyl bismuth dilaurate and dioctyl bismuth dilaurate, Bismuth ethylhexanoate, bismuth naphthenate, bismuth isodecanoate, neo Bismuth canate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth lin
  • Organic solvents having no functional group for example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and organic solvents such as aromatics such as toluene and xylene can be used.
  • the reaction temperature is usually 30 to 90 ° C., preferably 40 to 80 ° C.
  • the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.
  • the urethane (meth) acrylate-based compound (b1) used in the present invention preferably has 20 or less ethylenically unsaturated groups from the viewpoint of utilizing the adhesiveness with concrete which is a structural characteristic. Particularly preferred are those having 10 or less ethylenically unsaturated groups, and more preferred are those having 5 or less ethylenically unsaturated groups.
  • the lower limit of the number of ethylenically unsaturated groups is usually 2.
  • Reactive monomer (C) having one or more unsaturated groups for example, a monofunctional monomer, a bifunctional monomer, a trifunctional or higher monomer, other ethylenically unsaturated monomers, and the like can be used.
  • the monofunctional monomer a monomer containing one ethylenically unsaturated group is used.
  • styrene vinyl toluene, chlorostyrene, ⁇ -methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile.
  • a monomer containing two ethylenically unsaturated groups is used.
  • trifunctional or higher functional monomer a monomer containing three or more ethylenically unsaturated groups is used.
  • Examples of the other ethylenically unsaturated monomers include, in addition to the above, a Michael adduct of acrylic acid or 2-acryloyloxyethyl dicarboxylic acid monoester.
  • Examples of the Michael adduct of acrylic acid include acrylic acid dimer, methacrylic acid Examples include acid dimers, acrylic acid trimers, methacrylic acid trimers, acrylic acid tetramers, and methacrylic acid tetramers.
  • Examples of the 2-acryloyloxyethyl dicarboxylic acid monoester which is a carboxylic acid having a specific substituent include, for example, 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyl Examples thereof include oxyethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, and 2-methacryloyloxyethyl hexahydrophthalic acid monoester. Furthermore, oligoester acrylate is also mentioned.
  • a polyfunctional monomer of a bifunctional monomer and a trifunctional or higher monomer is preferable, and a polyfunctional (meth) acrylate compound (c1) is particularly preferable. It is.
  • the content of the reactive monomer (C) in the curable resin composition is 1 to 100 parts by weight when the total nonvolatile content of the binder polymer (A) component and the reactive oligomer (B) component is 100 parts by weight.
  • the amount is preferably 3 to 80 parts by weight, more preferably 5 to 70 parts by weight. If the content of the reactive monomer (C) is too small, the flexibility of the coating layer before pasting tends to be impaired, and the processability tends to be significantly impaired. If it is too much, the coating layer becomes too hard and impact resistance. Tends to decrease and become brittle.
  • Examples of the polymerization initiator (D) in the present invention include a thermal polymerization initiator and a photopolymerization initiator.
  • Examples of the thermal polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis2,4-dimethylvaleronitrile, Dimethyl-2,2'-azobisisoobtyrate, 1,1'-azobis (cyclohexane-1-carbonitrile), 1,1'-azobis (1-acetoxy1-phenylethane), 2,2'-azobis Azobis compounds such as (4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, ethyl methyl ketone peroxide, bis- (4-tert-butylcyclohexyl) peroxydicarbonate, diisopropylperoxy And peroxyd
  • the above azobis compounds are preferably used, and azobis compounds having a 10-hour half-life temperature of 50 ° C. or more are particularly preferable.
  • the azobis compounds having a 10-hour half-life temperature of 50 ° C. or more include 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), and 2,2′-azobis. (2-methylbutyronitrile), dimethyl 2,2'-azobis (2-methylpropinate) and the like.
  • photopolymerization initiator examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2 -Propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone
  • Acetophenones such as 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl etherkind; Nzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-
  • Benzophenones 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3 , 4-Dime Thioxanthones such as ru-9H-thioxanthone-9-one mesochloride; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphos And acylphosphine oxides such as fin oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
  • photopolymerization initiators can be used alone or in combination of two or more.
  • auxiliary agents include triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid.
  • Ethyl, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Etc. can be used in combination.
  • the content of the polymerization initiator (D) in the curable resin composition was 100 parts by weight of the total nonvolatile content of the binder polymer (A) component, the reactive oligomer (B) component, and the reactive monomer (C) component. Is preferably 0.1 to 30 parts by weight, particularly preferably 0.5 to 20 parts by weight, and further preferably 1 to 10 parts by weight.
  • the coating layer will be insufficiently cured and sufficient elasticity or hardness will not be obtained, and the film will tend to be brittle and will not function, and if the content is too large
  • the polymerization initiator (D) bleeds out during storage of the film before the reaction, and crystals tend to precipitate in the coating layer.
  • the curable resin composition in the laminated film for forming a concrete surface coating layer of the present invention may contain a filler (E).
  • a filler (E) By including the filler (E) in the curable resin composition, effects such as improvement in filling property, suppression of shrinkage during curing, and improvement in smoothness can be obtained.
  • the curable resin composition containing the filler (E) is not particularly limited as long as it is a resin composition that can be cured by heat and / or active energy rays, but preferably contains a compound having an unsaturated group. And more preferably a binder polymer (A), a reactive oligomer (B) having one or more unsaturated groups, and a reactive monomer (C) having one or more unsaturated groups. And a curable resin composition containing a polymerization initiator (D).
  • Examples of the filler (E) in the present invention include inorganic fillers and organic fillers.
  • Examples of the inorganic filler include talc, clay, silicon dioxide, silicic acid, diatomaceous earth, kaolin, mica, asbestos, gypsum, graphite, glass balloon, glass beads, calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, and calcium carbonate.
  • organic filler examples include, for example, melamine resins such as starch and melamine formaldehyde resin, crosslinked acrylic powder, acrylic ester / methacrylic ester copolymers, polymethyl (meth) acrylate resins, polystyrene resins, and the like. And biodegradable resins such as polylactic acid.
  • melamine resins such as starch and melamine formaldehyde resin
  • crosslinked acrylic powder acrylic ester / methacrylic ester copolymers
  • polymethyl (meth) acrylate resins polystyrene resins
  • biodegradable resins such as polylactic acid.
  • calcium carbonate powder is preferable from the viewpoint of affinity with lightweight cellular concrete (ALC).
  • the filler (E) is preferably a powder or fiber having an average particle size of 0.1 to 20 ⁇ m, particularly preferably a powder or fiber having an average particle size of 0.1 to 15 ⁇ m, and more preferably an average particle.
  • the “average particle diameter” here means the average value (median diameter) of the particle diameter at the time of integration (measurement), which is a laser diffraction particle size distribution measuring device (“SALD-2000J” manufactured by Shimadzu Corporation). ).
  • the filler (E) content in the curable resin composition is 1-1000 parts by weight when the total nonvolatile content of the binder polymer (A) component and the reactive oligomer (B) component is 100 parts by weight. It is preferably 5 to 500 parts by weight, more preferably 10 to 200 parts by weight. If the content of the filler (E) is too small, the shrinkage and fluidity of the resin become too large and the desired smoothness tends to be difficult to obtain. If the content is too large, the uncured film becomes brittle and bonded. However, the cured film tends to be brittle and the resin and filler tend to fall off the surface.
  • the curable resin composition substantially not containing the filler (E) is particularly referred to as a curable resin composition [i], and the curable resin composition containing the filler (E) is particularly curable resin composition. Indicated as [ii].
  • the content of the filler (E) in the curable resin composition [i] substantially not containing the filler (E) is preferably 5% by weight or less, particularly 3% by weight or less, and more preferably 1%.
  • the content is preferably not more than% by weight, and particularly preferably contains no filler (E).
  • the curable resin composition [ii] in the laminated film for forming a concrete surface coating layer of the present invention preferably further contains a foaming agent (F).
  • a foaming agent (F) in the curable resin composition [ii] the fillability of the laminated film for forming a concrete surface coating layer is further improved with respect to larger irregularities on the concrete surface.
  • a concrete base material particularly a base material having large and deep irregularities on the surface, such as a lightweight aerated concrete (ALC) board
  • ALC lightweight aerated concrete
  • a laminated film for forming a concrete surface covering layer is sufficient even for concave portions in millimeters scattered in the surface.
  • a smooth surface can be formed even in the periphery including such recesses by exhibiting filling properties.
  • the foaming agent (F) is preferably a pyrolytic foaming agent that generates gas by heating.
  • an inorganic compound or an organic compound can be used, and among them, an inorganic compound is preferable.
  • the inorganic compound include sodium hydrogen carbonate and sodium carbonate. Among them, sodium hydrogen carbonate is preferable.
  • the organic compounds include azodicarbonamide / 4,4′-oxybis, N, N′-dinitrosopentamethylenetetramine, azodicarbonamide, 4,4′-oxybis (benzenesulfonylhydrazide), N, N ′. -Dinitrosopentamethylenetetramine, azodicarbonamide and the like.
  • Such a foaming agent (F) is preferably a powder particle having an average particle size of 0.1 to 20 ⁇ m.
  • the “average particle diameter” here means the average value (median diameter) of the particle diameter at the time of integration (measurement), which is a laser diffraction particle size distribution measuring device (“SALD-2000J” manufactured by Shimadzu Corporation). ).
  • the content of the foaming agent (F) in the curable resin composition [ii] is such that the binder polymer (A) component and the reactive oligomer (
  • the total non-volatile content of component B) is 100 parts by weight, it is preferably 0.1 to 50 parts by weight, particularly preferably 0.2 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight. It is.
  • the content of the foaming agent (F) is too large, the porosity is remarkably increased, and the strength of the thermosetting layer tends to be lowered, and it is difficult to maintain the shape as a layer. Tends to be difficult to obtain.
  • the curable resin composition [i] or [ii] in the present invention may further include a plasticizer, an antioxidant, a solvent, a surface tension modifier, a stabilizer, a chain transfer agent, a surface activity, if necessary.
  • a plasticizer such as an antioxidant
  • a solvent such as an antioxidant
  • a surface tension modifier such as an antioxidant
  • a stabilizer such as an antioxidant
  • a chain transfer agent such as an agent
  • the laminated film for forming a concrete surface coating layer of the present invention has a structure in which a layer made of a curable resin composition (hereinafter also referred to as a curable resin composition layer) and a support film are laminated.
  • FIG. 1 is a cross-sectional view schematically showing an example of a laminated film for forming a concrete surface coating layer of the present invention, in which (1) is a curable resin composition layer, (2) is a support film, (10) Is a laminated film for forming a concrete surface coating layer of the present invention.
  • a protective film may be laminated on the side opposite to the support film of the curable resin composition layer.
  • the supporting film examples include a polyethylene terephthalate (PET) film, a polypropylene film, a polyethylene film, a polyethylene naphthalate film, a polyvinyl alcohol film, an ethylene vinyl alcohol copolymer film, or a paper having a resin layer laminated on the surface thereof. Is preferably used. Among these, it is particularly preferable to use a PET film or a paper having a resin layer laminated on the surface thereof in terms of heat resistance at the time of film formation and film curing.
  • the thickness of the support film is preferably 5 ⁇ m or more, particularly 10 to 100 ⁇ m, more preferably 20 to 50 ⁇ m.
  • a pattern intended for design can be provided on the surface of the support film, and this pattern can be transferred to a curable resin composition layer that covers the surface of the concrete after curing.
  • the protective film is used for the purpose of preventing transfer of a curable resin composition layer having adhesiveness to a support film when the laminated film for forming a concrete surface coating layer is formed into a roll.
  • protective films include polyethylene film, PET film, polypropylene film, polyvinyl alcohol film, ethylene vinyl alcohol copolymer film, polytetrafluoroethylene film, nylon film, release paper, among others.
  • Polyolefin films such as polyethylene film and polypropylene film are preferred.
  • the thickness of the protective film is preferably 5 ⁇ m or more, particularly 10 to 100 ⁇ m, more preferably 15 to 50 ⁇ m.
  • the laminated film for forming a concrete surface coating according to the present invention includes a support film, a layer composed of the curable resin composition [ii] containing the filler (E), and the curable material substantially not containing the filler (E).
  • stacked by this order layer structure may be sufficient.
  • FIG. 2 is a cross-sectional view schematically showing another example of the laminated film for forming a concrete surface coating layer of the present invention, and (11) in the figure is a curable resin composition substantially free of filler (E).
  • the layer which consists of curable resin composition [ii] containing a filler (E) may further contain the foaming agent (F).
  • a curable resin composition is uniformly applied to one side of a support film (2) and usually 50 to Examples thereof include a method of forming the curable resin composition layer (1) by drying for 5 to 60 minutes in an oven at 120 ° C. or sequentially increasing temperature. Moreover, when using a protective film, the said curable resin composition layer (1) is formed, and the method of carrying out pressure lamination of the protective film on the upper surface of this layer is then mentioned.
  • curable resin composition [ii] is uniformly apply
  • the curable resin composition [ii] is uniformly coated on one side of the support film (2), and is usually cured for 5 to 60 minutes in an oven that is usually 50 to 120 ° C. or higher in temperature to be curable.
  • an oven in which the resin composition layer (12) is formed and the curable resin composition [i] is uniformly applied to one side of the protective film and usually increases in temperature from 50 to 120 ° C. or sequentially, 5%
  • a method of laminating the curable resin composition layer (11) formed by drying for ⁇ 60 minutes is also included.
  • the content concentration of the filler (E) in the layer (12) made of the curable resin composition [ii] is supported in the thickness direction. It is also preferable that the film (2) side is inclined so as to have a higher density than the opposite side.
  • a method of inclining the content concentration of the filler (E) in the curable resin composition layer (12) in the thickness direction as described above for example, a plurality of curable resin compositions having different content concentrations of the filler (E) are used.
  • the method of forming (12) is mentioned.
  • the method of forming the said curable resin composition layer (11) or (12), and pressurizingly laminating a protective film on the upper surface of this layer (11) or (12) next. Can be mentioned.
  • the thickness of the curable resin composition layer is preferably 30 m or more, particularly 50 to 500 ⁇ m, more preferably 80 to 400 ⁇ m, and particularly preferably 100 to 300 ⁇ m.
  • the thickness of the curable resin composition layer is preferably 80 ⁇ m or more, particularly 100 to 500 ⁇ m, more preferably 150 to 300 ⁇ m.
  • the thickness of the curable resin composition layer is preferably 150 ⁇ m or more, In particular, 150 to 500 ⁇ m, more preferably 250 to 300 ⁇ m is preferable.
  • the thickness of the layer (11) made of the curable resin composition [i] is preferably 30 ⁇ m or more, particularly 50 to 500 ⁇ m. Further, the thickness of the layer (12) comprising the curable resin composition [ii] is preferably 50 ⁇ m or more, particularly 100 to 500 ⁇ m, more preferably 150 to 300 ⁇ m. Is preferred.
  • the curable resin composition is used in the laminated film (20) for forming a concrete surface coating layer of the present invention shown in FIG. 2, in the case where design is imparted to the coating layer obtained by curing the curable resin composition layer (11).
  • the total thickness of the layers (11) and (12) is preferably 150 ⁇ m or more, particularly 150 to 500 ⁇ m, more preferably 250 to 300 ⁇ m.
  • the thickness of the curable resin composition layer is too thin, the number of layers to be laminated becomes too large in order to obtain an appropriate thickness for mechanical protection on the concrete surface, resulting in a complicated lamination process and high cost. It tends to be too much, or a suitable thickness cannot be obtained for protection, and it is difficult to suppress damage to the concrete surface. Moreover, when this thickness is too thick, there exists a tendency for a coating layer to peel easily from the concrete surface, and there exists a tendency for cost to become high too much.
  • the thus obtained laminated film for forming a concrete surface covering layer of the present invention is suitably used for forming a covering layer for covering the surface of concrete, particularly for forming a covering layer for covering the surface of lightweight cellular concrete (ALC) board.
  • ALC lightweight cellular concrete
  • Lightweight cellular concrete (ALC) board has different surface properties depending on its manufacturing company or lot, but it may be coated on the surface as it is, or the surface is polished with sandpaper, etc. It is also possible to coat after exposing.
  • the concrete building material of the present invention has concrete and a concrete surface coating layer that covers the surface of the concrete, and the concrete surface coating layer is a curable resin in the laminated film for forming a concrete surface coating layer of the present invention. It can be formed by curing a layer made of the composition.
  • FIG. 3 is a cross-sectional view schematically showing a step of forming a coating layer on the concrete surface using the laminated film for forming a concrete surface coating layer of the present invention shown in FIG.
  • a laminate film (10) for forming a concrete surface coating layer is laminated, and the curable resin composition layer (1) is melted and bonded as shown in FIG.
  • a coating layer (4) which is a cured product, is formed on the surface (3a) of the concrete (3) as shown in FIG. 3 (d).
  • a support film (2) is peeled from a coating layer (4) as needed.
  • a method of forming a coating layer on the concrete surface using at least the curable resin composition layer (12) (see FIG. 2) containing the filler (E) in the curable resin composition layer Will be described.
  • a method of laminating the curable resin composition layer (11) for example, a support film and a curable resin composition layer (11) are used. Examples include a method of using a laminated film and laminating the laminated film on the concrete surface and then peeling the support film.
  • Coating layer forming method (a) In a coating layer forming method for forming a coating layer on a concrete surface, A laminated film (20) for forming a concrete surface covering layer, in which a support film and a layer (12) comprising a curable resin composition [ii] containing a filler (E) are laminated, is laminated on the concrete surface. Then, the curable resin composition layer (12) is brought into contact with the concrete surface, and the curable resin composition layer (12) is cured to form a coating layer on the concrete surface. Forming method.
  • Coating layer forming method (b) In a coating layer forming method for forming a coating layer on a concrete surface, A layer (11) comprising a curable resin composition [i] substantially free of filler (E) is laminated on the concrete surface, and a curable resin composition containing filler (E) thereon [ a layer (12) consisting of ii] is laminated and the curable resin composition layer (11) and the curable resin composition layer (12) are cured to form a coating layer on the concrete surface.
  • a coating layer forming method for forming a coating layer on a concrete surface A layer (11) composed of a curable resin composition [i] substantially free of filler (E) is laminated and cured on the concrete surface, and a curable resin composition containing filler (E) thereon.
  • a method for forming a coating layer comprising: forming a coating layer on the concrete surface by laminating and curing a layer (12) comprising the object [ii].
  • Coating layer forming method (d) In this coating layer forming method (d), for example, it can be carried out using the laminated film (20) for forming a concrete surface coating layer of the present invention shown in FIG.
  • a coating layer forming method for forming a coating layer on a concrete surface A support film (2), a layer (12) comprising a curable resin composition [ii] containing a filler (E), and a curable resin composition [i] substantially free of filler (E)
  • a laminated film for forming a concrete surface covering layer formed by laminating a layer (11) made of the above is laminated on the concrete surface, the curable resin composition layer (11) is brought into contact with the concrete surface, and the curable resin composition layer is formed.
  • a curable resin composition layer (12) is cured to form a coating layer on the concrete surface.
  • the laminated film for forming a concrete surface coating layer is also simply referred to as a laminated film.
  • the laminated film of the present invention may be laminated by simply placing the laminated film of the present invention on a lightweight concrete (ALC) board, or may be laminated by pasting the laminated film of the present invention.
  • the laminated film of the present invention is preferably bonded after preheating or drying a lightweight cellular concrete (ALC) board in advance.
  • a roll heated to a surface temperature of 70 ° C. or higher hereinafter also referred to as a hot roll
  • the laminated film for concrete surface coating layer formation has a protective film, it bonds together so that a curable resin composition layer may contact a lightweight aerated concrete (ALC) board, after peeling a protective film or after peeling.
  • the roll temperature is preferably 80 ° C. or more, particularly preferably 100 ° C. to 180 ° C., and further preferably 130 ° C. to 160 ° C. If the roll temperature is too low, the curable resin composition layer of the laminated film for forming a concrete surface coating layer will not be sufficiently softened and melted, and it will be difficult to penetrate the lightweight cellular concrete (ALC) board surface. There is a tendency to cause peeling of the resin composition layer. If the roll temperature is too high, the curable resin composition layer will melt too much and the viscosity will decrease, so that it will completely penetrate the lightweight aerated concrete (ALC) board, leaving no resin to cover the surface. When the curable resin composition contains a thermal polymerization initiator, curing of the curable resin composition proceeds during lamination, and sufficient penetration cannot be obtained. There is a tendency to cause delamination.
  • the weighted linear pressure of the hot roll when pressing the laminated film is preferably 0.1 to 100 kg / cm, particularly preferably 0.3 to 50 kg / cm, and further preferably 0.5 to 25 kg / cm.
  • the moving speed of the hot roll relative to the laminated film is preferably 0.01 to 20 m / min, particularly preferably 0.1 to 15 m / min, and more preferably 0.2 to 10 m / min. If the weighted linear pressure of the hot roll is too small or the moving speed of the hot roll is too high, the curable resin composition layer of the laminated film will not sufficiently penetrate the lightweight cellular concrete (ALC) board surface, and after curing There is a tendency to cause peeling of the curable resin composition layer.
  • ALC lightweight cellular concrete
  • the curable resin composition layer completely penetrates into the lightweight cellular concrete (ALC) board and covers the surface. Therefore, there is a tendency that no resin content remains.
  • the roll used in the case of bonding is not restricted to said heat roll, The roll which is not heated (namely, atmospheric temperature) can also be used.
  • the curable resin composition of this laminated film for forming a concrete surface coating layer is used. It is also possible to stack physical layers.
  • the second concrete surface coating layer is formed in the same manner on the first curable resin composition layer exposed by peeling off the support film of the laminated film for forming the first concrete surface coating layer bonded above.
  • a laminated film may be laminated to laminate the first curable resin composition layer and the second curable resin composition layer.
  • the light weight is reduced in the same manner as described above. It is also possible to bond to the surface of cellular concrete (ALC) board.
  • ALC cellular concrete
  • the laminated film for forming a concrete surface coating layer is laminated on the concrete by performing the above lamination (bonding). And after making a curable resin composition layer contact with a concrete surface, it can carry out by hardening a curable resin composition layer.
  • a thermal polymerization initiator as a polymerization initiator (D)
  • D polymerization initiator
  • the first method is a method in which a laminated film for forming a concrete surface coating layer is pressed against the concrete surface with a hot roll to cure the curable resin composition layer.
  • the heat roll is preferably disposed on the laminated film and presses the concrete surface through the laminated film.
  • the thermal roll for example, a single roll machine having one roll, a continuous roll machine in which a plurality of rolls are arranged in a direction crossing the roll axis, or the like is used.
  • the plurality of rolls in the continuous roll machine are preferably arranged with the surface temperature gradually set to be large so that the amount of heat applied to the laminated film gradually increases.
  • a material which comprises a roll a metal or rubber
  • gum for example, A metal is preferable from the point that temperature control is easy.
  • the number of rolls in the continuous roll machine is usually 2 to 10, preferably 3 to 8, and particularly preferably 4 to 6.
  • the heat roll to be used examples include a smooth roll having a smooth outer peripheral surface, an embossing roll having irregularities formed on the outer peripheral surface, and the like. It is preferable to use it.
  • the depth of the recess in the embossing roll is, for example, 0.001 to 1 mm, preferably 0.005 to 0.5 mm.
  • the surface temperature of the hot roll when pressing the concrete surface through the laminated film is preferably 70 ° C. or higher, particularly preferably 100 ° C. to 180 ° C., more preferably 130 ° C. to 160 ° C.
  • the curable resin composition layer is insufficiently cured and tends to cause peeling of the curable resin composition layer after curing.
  • the linear pressure of the hot roll when pressing the concrete surface through the laminated film is preferably 0.01 to 10 kg / cm, particularly preferably 0.05 to 5 kg / cm, more preferably 0.1 to 2 kg / cm. It is.
  • the moving speed of the hot roll relative to the laminated film is preferably 0.01 to 20 m / min, particularly preferably 0.05 to 15 m / min, and further preferably 0.1 to 10 m / min. If the linear pressure of the hot roll is too small or the moving speed of the hot roll is too high, the curing of the curable resin composition layer becomes insufficient, and tends to cause peeling of the curable resin composition layer after curing. There is.
  • the curable resin composition layer completely penetrates into the concrete such as lightweight aerated concrete (ALC) board, and becomes on the surface. There is a tendency that a resin component for coating does not remain.
  • ALC lightweight aerated concrete
  • the second method is a method in which the laminated film for forming a concrete surface coating layer is pressed against the concrete surface with a hot plate to cure the curable resin composition layer.
  • the hot plate is preferably disposed on the laminated film and presses the concrete surface through the laminated film.
  • the heat plate to be used examples include a flat plate having a smooth surface in contact with the laminated film, an embossed plate having irregularities formed on the surface in contact with the laminated film, and the like, but can provide design properties by forming irregularities on the coating layer. It is preferable to use an embossed plate in terms of points.
  • the depth of the recess in the embossed plate is, for example, 0.001 to 1 mm, preferably 0.005 to 0.5 mm.
  • the surface temperature of the hot plate when pressing the concrete surface through the laminated film is preferably 70 ° C. or higher, particularly preferably 100 ° C. to 180 ° C., more preferably 130 ° C. to 160 ° C.
  • the surface temperature of the hot plate is too low, curing of the curable resin composition layer becomes insufficient and tends to cause peeling of the curable resin composition layer after curing.
  • the pressure of the hot plate when pressing the concrete surface through the laminated film is preferably 0.5 to 500 kgf / cm 2 , particularly preferably 1 to 100 kg / m 2 , more preferably 2 to 80 kg / m 2 . .
  • the pressing time is preferably 1 to 120 minutes, particularly preferably 3 to 60 minutes, and further preferably 5 to 30 minutes.
  • the curable resin composition layer is not sufficiently cured, and tends to cause peeling of the curable resin composition layer after curing.
  • the pressure of the hot plate is too large or the pressing time is too long, the curable resin composition layer completely penetrates into the concrete such as lightweight cellular concrete (ALC) board and covers the surface. There is a tendency that no resin remains.
  • ALC lightweight cellular concrete
  • the third method is a method of forming a coating layer on the concrete surface by curing the curable resin composition layer in a high-temperature atmosphere.
  • the ambient temperature is 70 ° C. or higher, particularly preferably 100 ° C. to 180 ° C., and more preferably 130 ° C. to 160 ° C.
  • Examples of the method for curing the curable resin composition layer in a high-temperature atmosphere include, for example, a method in which a laminated film for forming a concrete surface coating layer is left in a thermostat adjusted to the above atmospheric temperature, and the above atmospheric temperature is adjusted.
  • multilayer film for concrete surface coating layer formation in the made atmosphere furnace is mentioned.
  • This third method may be combined with the first method or the second method described above. Further, the heat roll used in the first method or the heat plate used in the second method is changed to a roll, an emboss roll, a flat plate or an emboss plate whose surface temperature is less than the above temperature, and a concrete surface coating layer forming laminate The third method may be performed while pressing the film against the concrete surface or after pressing.
  • the curable resin composition layer of the laminated film for forming a concrete surface coating layer is brought into contact with the concrete surface, and then placed in a bag made of a single layer film or a multilayer film, and the atmosphere of the package sealed under reduced pressure.
  • the coating layer is formed on the concrete surface by setting the temperature to 90 ° C. or higher.
  • the bag into which the laminate of the concrete and the laminated film for forming the concrete surface coating layer is a bag made of a single layer film or a multilayer film.
  • a thermoplastic resin film can be used as the film constituting the single layer film or the multilayer film.
  • the thermoplastic resin include a polyolefin film, a polyester film, a polyamide film, a polyurethane film, and a polyvinyl alcohol film.
  • Examples of the resin constituting the polyolefin film include homopolymers such as polypropylene, polybutene-1, high density polyethylene, medium density polyethylene, low density polyethylene, linear short chain branched polyethylene (LLDPE), and propylene.
  • homopolymers such as polypropylene, polybutene-1, high density polyethylene, medium density polyethylene, low density polyethylene, linear short chain branched polyethylene (LLDPE), and propylene.
  • Polymers, and further graft-modified with carboxylic acids such as maleic anhydride, propylene mainly containing ethylene, butene-1,4-methylpentene-1,1-hexene, 1-octene, 5-ethylidene- Copolymers with 2-norbornene, 5-methylene-2-norbornene, styrene, vinyl acetate, methyl acrylate, ethyl acrylate, acrylic acid, methyl methacrylate, ethyl methacrylate, methacrylic acid, glycidyl methacrylate, etc.
  • carboxylic acids such as maleic anhydride, propylene mainly containing ethylene, butene-1,4-methylpentene-1,1-hexene, 1-octene, 5-ethylidene- Copolymers with 2-norbornene, 5-methylene-2-norbornene, styrene, vinyl acetate, methyl acryl
  • a copolymer with acrylic acid or methacrylic acid may be crosslinked with sodium, zinc, aluminum or the like, and a copolymer with vinyl acetate is a part of vinyl acetate component or All may be saponified.
  • Polyethylene may be graft-modified with a carboxylic acid such as maleic anhydride.
  • a polypropylene film, a polyvinyl chloride film, a polyvinylidene chloride film, and a fluorine film are preferable.
  • resin which comprises a polyester-type film it is comprised from an acid component and a glycol component.
  • the acid component include terephthalic acid, oxalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid.
  • Dimer acid maleic anhydride, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, dicarboxylic acids such as cyclohexanedicarboxylic acid, oxycarboxylic acids such as 4-hydroxybenzoic acid, ⁇ -caprolactone, lactic acid, etc. It is done.
  • glycol component examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, cyclohexanedimethanol, triethylene glycol, polyethylene glycol, polypropylene glycol, And glycols such as polytetramethylene glycol.
  • a polyester resin is obtained by copolymerizing the above acid (component) and glycol (component).
  • the combination of both components is not particularly limited, and those copolymerized in any combination can be used.
  • the polyester polyethylene terephthalate, polyethylene naphthalate, polycyclohexylene dimethylene terephthalate is preferably used. Furthermore, polyethylene terephthalate is particularly preferably used.
  • Single layer film or multilayer film used in the present invention may be a mixture of two or more thermoplastic resins.
  • the monolayer film or the multilayer film used in the present invention includes an ultraviolet absorber, an antioxidant, an antistatic agent, a surfactant, a pigment, a fluorescent brightening agent, and the like, and silica, calcium carbonate, titanium oxide, and the like.
  • Organic particles containing inorganic particles, acrylic acid, styrene and the like as constituent components may be appropriately contained as necessary.
  • the monolayer film or the multilayer film used in the present invention is preferably subjected to a stretching treatment, and for example, a uniaxially stretched film or a biaxially stretched film is preferably used.
  • the multilayer film used in the present invention has a structure in which two or more kinds of thermoplastic resin layers are laminated, and a vapor deposition layer or an adhesive layer may be interposed between the thermoplastic resin layers.
  • a metal or metal oxide used for a vapor deposition layer metals or metal oxides, such as aluminum, gold
  • aluminum, gold, silver, and tin are preferably used, and aluminum is particularly preferably used from the viewpoint of cost.
  • the thickness of the deposited layer is usually 50 to 1000 mm, particularly 200 to 1000 mm.
  • a vapor deposition method of a metal or metal oxide for example, a general vacuum vapor deposition method such as a sputtering method, an ion plating method, a resistance heating vapor deposition method, a high frequency induction heating vapor deposition method, or an electron beam heating vapor deposition method can be used.
  • a general vacuum vapor deposition method such as a sputtering method, an ion plating method, a resistance heating vapor deposition method, a high frequency induction heating vapor deposition method, or an electron beam heating vapor deposition method can be used.
  • the adhesive in the adhesive layer include an organic titanium compound, an isocyanate compound, and a polyester compound.
  • a known method can be adopted as a method for producing a single layer film or a multilayer film used in the present invention.
  • a film is formed by casting a solution of a thermoplastic resin on a metal surface such as a drum or an endless belt.
  • the film can be formed by a casting molding method or a melt molding method by melt extrusion using an extruder.
  • the thickness of the monolayer film used in the present invention is usually 5 to 200 ⁇ m, and preferably 10 to 100 ⁇ m.
  • the thickness of the multilayer film is usually 5 to 200 ⁇ m, particularly 10 to 100 ⁇ m. If the thickness is too thin, tearing or the like tends to occur at the time of processing. Conversely, if the thickness is too thick, not only the workability is lowered but also the economy tends to be uneconomical.
  • a seal layer on the inner surface of the bag.
  • a polyolefin resin layer is preferable from the viewpoint of seal strength, and among them, polypropylene, high density polyethylene, low density polyethylene, ethylene-vinyl acetate resin, and the like are preferably used.
  • a film is prepared separately from the above resin, and such a film may be laminated by using an adhesive or the like on the inner surface of the bag, or on the inner surface of the bag. Direct extrusion may be used for lamination.
  • laminating the sealing layer as a film laminating it as an unstretched film is advantageous in terms of obtaining sealing properties.
  • the thickness of the seal layer is usually 10 to 100 ⁇ m, and particularly preferably 20 to 80 ⁇ m.
  • the degree of vacuum in the package is preferably 100 Pa or less, more preferably 10 Pa or less, and particularly preferably 5 Pa or less.
  • the laminate When putting a laminate of concrete and a laminate film for forming a concrete surface coating layer into a bag made of the above-mentioned single layer film or multilayer film, the laminate may be put in the bag as it is or in contact with the laminate film.
  • a flat plate with a smooth surface, or an embossed plate with irregularities formed on the surface in contact with the laminated film may be put in the bag in a state where it is placed on the laminated film of the laminated body.
  • an embossed plate in terms of providing designability by forming irregularities on the coating layer.
  • the depth of the recess in the embossed plate is, for example, 0.001 to 1 mm, preferably 0.005 to 0.5 mm.
  • a flat plate, an embossed plate, or the like may be placed on the laminated film side of the packaging body in which the laminated body is put in a bag, and the following heat treatment or active energy ray irradiation may be performed.
  • the ambient temperature of the package in which the laminate is sealed in the bag is set. Set to 90 ° C or higher.
  • the ambient temperature is preferably 90 to 180 ° C, particularly preferably 100 ° C to 180 ° C, and more preferably 130 ° C to 160 ° C.
  • Examples of a method for adjusting the ambient temperature of the package to such a temperature include, for example, a method of leaving the package in a thermostat adjusted to the ambient temperature, and the packaging in an atmosphere furnace adjusted to the ambient temperature. The method of moving the body is mentioned.
  • the time for which the package is kept in such a temperature atmosphere is preferably 1 to 120 minutes, particularly preferably 3 to 60 minutes, and further preferably 5 to 30 minutes.
  • the curable resin composition layer contains a photopolymerization initiator
  • a method for curing the curable resin composition layer will be described.
  • the curable resin composition layer contains a photopolymerization initiator
  • the curable resin composition layer of the laminated film for forming a concrete surface coating layer is irradiated with active energy rays.
  • the active energy rays may be irradiated from the support film side of the laminated film for forming a concrete surface coating layer, or may be irradiated through a flat plate or an embossed plate on the support film.
  • the resin composition layer may be directly irradiated.
  • rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X-rays and ⁇ rays, electron beams, proton rays, neutron rays and the like can be used.
  • Curing by ultraviolet irradiation is advantageous because of the availability of the irradiation device and the price.
  • a high pressure mercury lamp that emits light in a wavelength range of 150 to 450 nm
  • an ultra high pressure mercury lamp a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless lamp, an LED lamp, etc.
  • Examples include a method of irradiating about 100 to 3000 mJ / cm 2 . After the irradiation with ultraviolet rays, if necessary, heating can be performed to complete the curing.
  • a laminate having a laminated film for forming a concrete surface coating layer in which the curable resin composition layer is cured can be taken out of the bag. It can also be left in the bag until use. By keeping it in the bag until use, damage during transportation and storage, dust derived from concrete, and the like can be prevented.
  • the laminated film for forming a concrete surface coating layer After being laminated on a lightweight cellular concrete (ALC) board, the laminated film for forming a concrete surface coating layer that has undergone a curing reaction leaves an unnecessary part due to the resin protruding from the end face of the board due to its load, etc. In some cases, this unnecessary portion may be removed by cutting or cutting. Furthermore, a resin composition that is the same as or similar to the curable resin composition used in the present invention, in a portion where a laminated film for forming a concrete surface covering layer is missing on a part of the end face, or a portion that cannot be laid during processing.
  • the binder polymer (A) constituting the curable resin composition used in the present invention or a resin similar to the binder polymer (A) may be supplemented by coating or the like. Through the above steps, the concrete building material of the present invention can be obtained.
  • ⁇ Binder polymer (A)> (A1): Polymethyl methacrylate (glass transition temperature: 105 ° C.) (“Dianar BR-83” manufactured by Mitsubishi Rayon Co., Ltd.)
  • Reactive oligomer (B) having one or more unsaturated groups The following were prepared as reactive oligomers (B1).
  • C ⁇ Reactive monomer having one or more unsaturated groups>
  • C1 Methoxypolyethylene glycol methacrylate (“M-90G” manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • C2 Condensation product of pentaerythritol and acrylic acid (corresponding to “biscoat 300” manufactured by Osaka Organic Chemical Industry Co., Ltd., trifunctional or higher monomer)
  • D1 2,2′-azobisisobutyronitrile (“V-60” manufactured by Wako Pure Chemical Industries, Ltd.)
  • D2′-azobisisobutyronitrile (“V-60” manufactured by Wako Pure Chemical Industries, Ltd.)
  • D2 1,1′-azobis (cyclohexane-1-carbonitrile (“V-40” manufactured by Wako Pure Chemical Industries, Ltd.)
  • Example 1 A resin solution obtained by diluting the binder polymer (A1) to 40% with ethyl acetate and an oligomer solution obtained by diluting the reactive oligomer (B1) to 70% with 2-butanone are combined with the binder polymer (A1) and the reactive oligomer (B1). ) Is mixed so that the weight ratio of the nonvolatile content is 40:60, and then the reactive monomer (C1) is further added to the total nonvolatile content of the binder polymer (A1) and the reactive oligomer (B1) of 100 parts. It mixed so that it might become 20 parts.
  • the polymerization initiator (D1) is mixed so that the nonvolatile content of the mixture of (A1), (B1), (C1) is 2 parts with respect to 100 parts of the nonvolatile content, and the non-volatile content becomes 56%.
  • a resin composition [i-1] solution was obtained.
  • This curable resin composition [i-1] solution was continuously cast on a polyester film [III] having a thickness of 25 ⁇ m by a comma coater set to a gap width of 0.5 mm, and this was further continuously treated by 70%. By drying for 12 minutes at 90 ° C. and 6 minutes at 90 ° C., a curable resin composition layer [I-1] having a thickness of 220 ⁇ m was formed. Simply referred to as a laminated film).
  • a concrete building material [ ⁇ -1] for evaluation was obtained as follows. That is, the concrete panel (“Hebel Power Board Flat Panel” manufactured by Asahi Kasei Construction Materials Co., Ltd. (thickness: 37 mm)) (P), which has been dried at 80 ° C. for 24 hours and then cooled to room temperature, The laminated film (IV-1) for forming the surface coating layer was laminated so that the curable resin composition layer [I-1] surface side was overlapped, and this was pressed while pressing it with a rubber roll heated to 150 ° C. at a linear pressure of 2 kg / cm. Lamination was performed at a speed of 25 m / min (first lamination).
  • the polyester film [III] is peeled off from the laminated film (IV-1), and another concrete surface produced in the same manner as described above on the curable resin composition layer [I-1].
  • Laminating films for forming a coating layer were laminated so that the curable resin composition layer [I-1] surface side was overlapped, and this was similarly applied to a rubber roll heated to 150 ° C. while pressing it at a linear pressure of 2 kg / cm. Lamination was performed at a rate of 25 m / min (second lamination) to obtain an uncured panel laminate.
  • the surface of the hardened film (coating layer) side of the concrete building material [ ⁇ -1] obtained above is smooth, the polyester film [III] is peeled off, and a commercially available acrylic lacquer is applied to this surface twice.
  • a flat design surface rich in gloss was obtained.
  • two straight cuts with a cutter knife are put on the cured film surface in a crossed shape, and a commercially available gum tape is pasted so as to cover the intersection of the cuts, and a roll of 5 kg is reciprocated 10 times. And completely bonded.
  • this gummed tape was peeled from the end portion at a constant speed of 10 m / min, no peeling of the cured film (coating layer) was observed at the cut portion.
  • Example 2 Using the laminated film (IV-1) for forming a concrete surface coating layer obtained in Example 1, a concrete building material for evaluation [ ⁇ -2] was obtained as described below. That is, the concrete panel (“Hebel Power Board Flat Panel” manufactured by Asahi Kasei Construction Materials Co., Ltd. (thickness: 37 mm)) (P), which has been dried at 80 ° C. for 24 hours and then cooled to room temperature, The laminated film (IV-1) for forming the surface coating layer is laminated so that the curable resin composition layer [I-1] surface side is overlapped, and the polyester film of the laminated film for forming the concrete surface coating layer (IV-1) [ III], a smooth aluminum plate having a thickness of 10 mm was laminated to obtain a laminate.
  • the concrete panel (“Hebel Power Board Flat Panel” manufactured by Asahi Kasei Construction Materials Co., Ltd. (thickness: 37 mm)) (P), which has been dried at 80 ° C. for 24 hours and then cooled to room temperature
  • This laminate is inserted into a vacuum packaging bag formed by laminating and laminating aluminum foil and polyethylene film, and the vacuum packaging bag is decompressed to 600 Pa with a vacuum packaging machine and sealed (enclosed).
  • the concrete panel (P), the laminated film (IV-1) for forming a concrete surface covering layer, and the aluminum plate were brought into close contact with each other.
  • the reduced pressure packaging bag sealed (enclosed) in a reduced pressure state, and the laminate of the concrete panel (P), the laminated film for forming a concrete surface covering layer (IV-1), and the aluminum plate, which are in close contact with each other.
  • the curable resin composition layer [I-1] was infiltrated and adhered to the concrete panel (P) by being left in a thermostatic oven heated to 130 ° C. for 1 hour and cured. Thereafter, the decompression packaging bag was opened, and the aluminum plate was removed to obtain a concrete building material for evaluation [ ⁇ -2] in which a coating layer was formed on the surface of the concrete panel (P).
  • the surface of the hardened film (coating layer) side of the concrete building material [ ⁇ -2] obtained above is smooth, the polyester film [III] is peeled off, and a commercially available acrylic lacquer is applied to this surface twice.
  • a flat design surface rich in gloss was obtained.
  • two straight cuts with a cutter knife are put on the cured film surface in a crossed shape, and a commercially available gum tape is pasted so as to cover the intersection of the cuts, and a roll of 5 kg is reciprocated 10 times. And completely bonded.
  • this gummed tape was peeled from the end portion at a constant speed of 10 m / min, no peeling of the cured film (coating layer) was observed at the cut portion.
  • the concrete building material [ ⁇ -2] was fixed in the air with the surface on which the cured film (coating layer) was not laminated facing up, and the panel center was struck 5 times with bare hands. However, from the cured film (coating layer) surface side, no debris was removed.
  • Example 3 A resin solution obtained by diluting the binder polymer (A1) to 40% with ethyl acetate and an oligomer solution obtained by diluting the reactive oligomer (B1) to 70% with 2-butanone are combined with the binder polymer (A1) and the reactive oligomer (B1). ) was mixed so that the weight ratio of non-volatile content was 37:63. Next, the polymerization initiator (D1) is mixed so as to be 2 parts with respect to 100 parts of the nonvolatile content of the mixture of (A1) and (B1), and the nonvolatile content concentration becomes 56%. [I-2] A solution was obtained.
  • a curable resin composition layer [I-2] having a thickness of 230 ⁇ m was formed on a polyester film [III] having a thickness of 25 ⁇ m in the same manner as in Example 1.
  • a laminated film (IV-2) for forming a concrete surface coating layer was obtained.
  • a concrete building material for evaluation [ ⁇ -3] was obtained in the same manner as in Example 1 except that this laminated film (IV-2) for forming a concrete surface coating layer was used and the heating temperature of the hot roll was changed to 175 ° C. It was.
  • the surface of the hardened film (coating layer) side of the concrete building material [ ⁇ -3] obtained above is smooth, the polyester film [III] is peeled off, and a commercially available acrylic lacquer is applied to the surface twice.
  • a flat design surface rich in gloss was obtained.
  • the concrete building material [ ⁇ -3] was fixed in the air with the surface side on which the cured film (coating layer) was not laminated facing up, and the panel center was struck 5 times with bare hands. However, from the cured film (coating layer) surface side, no debris was removed.
  • Example 4 A resin solution obtained by diluting the binder polymer (A1) to 40% with ethyl acetate and an oligomer solution obtained by diluting the reactive oligomer (B1) to 70% with 2-butanone are combined with the binder polymer (A1) and the reactive oligomer (B1). ) Is mixed so that the weight ratio of the nonvolatile content is 40:60, and the reactive monomer (C2) is further added to 100 parts of the nonvolatile content of the binder polymer (A1) and the reactive oligomer (B1). The mixture was mixed to 12 parts.
  • the polymerization initiator (D2) is mixed so that the nonvolatile content of the mixture of (A1), (B1), and (C2) is 2 parts with respect to 100 parts of the nonvolatile content.
  • a resin composition [i-3] solution was obtained.
  • the surface of the hardened film (coating layer) side of the concrete building material [ ⁇ -4] obtained above is smooth, the polyester film [III] is peeled off, and a commercially available acrylic lacquer is applied to the surface twice.
  • a flat design surface rich in gloss was obtained.
  • the concrete building material [ ⁇ -4] was fixed in the air with the surface side on which the cured film (coating layer) was not laminated facing up, and the panel center was struck 5 times with bare hands. However, from the cured film (coating layer) surface side, no debris was removed.
  • Examples 5 to 13 In the following Examples 5 to 13, the following laminated film for forming a concrete surface coating layer was used.
  • a resin solution obtained by diluting the binder polymer (A1) to 40% with ethyl acetate and an oligomer solution obtained by diluting the reactive oligomer (B1) to 70% with 2-butanone are combined with the binder polymer (A1) and the reactive oligomer (B1).
  • ) Is mixed so that the weight ratio of the nonvolatile content is 40:60, and then the reactive monomer (C1) is further added to the total nonvolatile content of the binder polymer (A1) and the reactive oligomer (B1) of 100 parts. It mixed so that it might become 20 parts.
  • the polymerization initiator (D1) is mixed so that the nonvolatile content of the mixture of (A1), (B1), (C1) is 2 parts with respect to 100 parts of the nonvolatile content, and the non-volatile content becomes 56%.
  • a resin composition [i-1] solution was obtained.
  • This curable resin composition [i-1] solution was continuously cast on a polyester film [III] having a thickness of 25 ⁇ m by a comma coater set to a gap width of 0.5 mm, and this was further continuously treated by 70%. By drying for 12 minutes at 90 ° C. and 6 minutes at 90 ° C., a curable resin composition layer [I-1] having a thickness of 220 ⁇ m was formed to obtain a laminated film (IV-1) for forming a concrete surface coating layer .
  • the curable resin composition [ii-1] solution 5 parts with respect to 100 parts in total of the nonvolatile content of the binder polymer (A1) and the reactive oligomer (B1) in the [ii-1] solution;
  • a curable resin composition [ii] was added by adding a foaming agent (F) mainly composed of sodium hydrogen carbonate (“Selbon SC-K” manufactured by Eiwa Kasei Kogyo Co., Ltd.) and stirring until further uniform.
  • F foaming agent
  • This curable resin composition [ii-2] solution was continuously cast on a polyester film [III] having a thickness of 25 ⁇ m in the same manner as the curable resin composition [i-1] solution.
  • a curable resin composition layer [II-2] having a thickness of 250 ⁇ m was formed to obtain a laminated film (IV-5) for forming a concrete surface coating layer.
  • Example 5 Using the obtained laminated films (IV-1) and (IV-4), a concrete building material for evaluation [ ⁇ -5] was obtained as described below. That is, the above laminate is applied to the surface on the outer wall side of a concrete panel (“Hebel Power Board Flat Panel” (thickness 37 mm) manufactured by Asahi Kasei Construction Materials Co., Ltd.) (P) after drying at 80 ° C. for 24 hours and cooling to room temperature.
  • the film (IV-1) was laminated so that the curable resin composition layer [I-1] surface side overlaps, and this was pressed at a linear pressure of 2 kg / cm with a rubber roll heated to 150 ° C., at a speed of 0.25 m / min. (First lamination).
  • the polyester film [III] is peeled from the laminated film (IV-1), and the laminated film (IV-4) is further cured on the curable resin composition layer [I-1].
  • the resin composition layer [II-1] is laminated so that the surface side is overlapped, and this is laminated at a speed of 0.25 m / min while pressing with a rubber roll heated to 150 ° C. with a linear pressure of 2 kg / cm. (Second lamination) An uncured panel laminate having a curable resin composition layer [II-1] was obtained.
  • the curable resin composition layers [I-1] and [II-1] are cured by placing them in a thermostatic chamber heated to 130 ° C. for 1 hour, and a concrete building material for evaluation [ ⁇ - 5] was obtained.
  • the surface of the hardened film side of the concrete building material [ ⁇ -5] obtained above is smooth, the polyester film [III] is peeled off, and a commercially available acrylic lacquer is applied to the surface by spray coating twice. A flat design surface rich in gloss was obtained.
  • two straight cuts with a cutter knife are put on the cured film surface in a crossed shape, and a commercially available gum tape is pasted so as to cover the intersection of the cuts, and a roll of 5 kg is reciprocated 10 times. And completely bonded. When this gummed tape was peeled from the end portion at a constant speed of 10 m / min, no peeling of the cured film was observed at the cut portion.
  • the panel laminate [ ⁇ -5] was fixed in the air with the surface side where the cured film was not laminated facing up, and the panel surface center was struck 5 times with bare hands. Debris etc. were not removed from the surface side.
  • this panel laminate [ ⁇ -5] is cut with an electric saw equipped with a lightweight cellular concrete blade so that the cut end is perpendicular to the bonding surface of the panel laminate [ ⁇ -5], Further, the cross section was polished with # 40 sandpaper, followed by # 400 sandpaper, and the concrete panel surface and the curable resin composition layers [I-1] and [II-1] laminated thereon were formed. The boundary was clearly confirmed with a magnifying glass, and the thickness from the average line of the boundary to the surface of the curable resin composition layer [II-1] was measured to be 364 ⁇ m.
  • the average line of the above boundary is obtained by accumulating the position coordinates of the irregularities on the surface of the concrete panel (ALC) as the base material when looking at a somewhat large cross section, for example, a cross section of 5 to 10 cm.
  • the horizontal reference axis is such that the sum of the position coordinates obtained is zero.
  • Example 6 Using the laminated films (IV-1) and (IV-4), a concrete building material for evaluation [ ⁇ -6] was obtained using the laminated films (IV-1) and (IV-4) in the same manner as in Example 5 except that the concrete panel whose surface was polished was used. It was. Specifically, after drying for 24 hours at 80 ° C., the surface on the outer wall side of the concrete panel (“Hebel Power Board Flat Panel” (thickness 37 mm) manufactured by Asahi Kasei Construction Materials Co., Ltd.) (P), cooled to room temperature, Using a grinder equipped with # 40 sandpaper, it was uniformly polished and cut to a depth of 3 mm to expose more foamed bubbles than the surface before polishing. This new surface was laminated so that the curable resin composition layer [I-1] surface side of the laminated film (IV-1) overlaps, and thereafter, the concrete building material for evaluation [ ⁇ - 6] was obtained.
  • the surface on the outer wall side of the concrete panel (“Hebel Power Board Flat Panel” (thickness
  • the surface of the cured film side of the concrete building material [ ⁇ -6] obtained above is smooth, the polyester film [III] is peeled off, and a commercially available acrylic lacquer is applied to the surface by spray coating twice. A flat design surface rich in gloss was obtained.
  • two straight cuts with a cutter knife are put on the cured film surface in a crossed shape, and a commercially available gum tape is pasted so as to cover the intersection of the cuts, and a roll of 5 kg is reciprocated 10 times. And completely bonded. When this gummed tape was peeled from the end portion at a constant speed of 10 m / min, no peeling of the cured film was observed at the cut portion.
  • the concrete building material [ ⁇ -6] was fixed in the air with the surface side where the cured film was not laminated facing up, and the panel center was struck 5 times with bare hands. Debris etc. were not removed from the surface side.
  • the concrete building material [ ⁇ -6] is cut with an electric saw equipped with a lightweight foam concrete blade so that the cut end is perpendicular to the bonding surface of the concrete building material [ ⁇ -6], Further, the cross section was polished with # 40 sandpaper, followed by # 400 sandpaper, and the concrete panel surface and the curable resin composition layers [I-1] and [II-1] laminated thereon were formed. The boundary was clearly confirmed with a magnifying glass, and the thickness from the average line of the boundary to the surface of the curable resin composition layer [II-1] was measured to be 237 ⁇ m.
  • Example 7 The uncured panel laminate obtained in Example 5 was cured as follows to obtain a concrete building material [ ⁇ -7] for evaluation. That is, the area is the same as the area of the uncured panel laminate, preheated to 130 ° C. in advance, and the engraved iron plate is placed on the curable resin composition layer [II-1] side of the panel laminate, Further, by applying a load of 50 kgf / cm 2 and leaving it in a constant temperature bath at 130 ° C. for 60 minutes to cure the curable resin composition layers [I-1] and [II-1], A concrete building material [ ⁇ -7] was obtained. The surface of the iron plate is engraved in a staggered pattern with squares having a depth of 100 ⁇ m and a side of 5 mm arranged at equal intervals.
  • polyester film [III] of the concrete building material [ ⁇ -7] obtained above is peeled off and sprayed with a commercially available acrylic lacquer on this surface twice, it is rich in gloss and has a staggered lattice. A surface having an uneven design was obtained.
  • two straight cuts with a cutter knife are put on the cured film surface in a crossed shape, and a commercially available gum tape is pasted so as to cover the intersection of the cuts, and a roll of 5 kg is reciprocated 10 times. And completely bonded.
  • this gummed tape was peeled from the end portion at a constant speed of 10 m / min, no peeling of the cured film was observed at the cut portion.
  • the concrete building material [ ⁇ -7] was fixed in the air with the surface on which the cured film was not laminated facing up, and the center of the panel surface was struck 5 times with bare hands. Debris etc. were not removed from the surface side.
  • this concrete building material [ ⁇ -7] is cut with an electric saw equipped with a lightweight foam concrete blade so that the cut end is perpendicular to the bonding surface of the concrete building material [ ⁇ -7], Further, the cross section was polished with # 40 sandpaper, followed by # 400 sandpaper, and the concrete panel surface and the curable resin composition layers [I-1] and [II-1] laminated thereon were formed. The boundary was clearly confirmed with a magnifying glass, and the thickness from the average line of the boundary to the surface of the curable resin composition layer [II-1] was measured. As a result, the thickness of the thick portion of the staggered lattice was 387 ⁇ m. The thickness of the thin part was 292 ⁇ m.
  • Example 8 The uncured panel laminate obtained in Example 6 was cured as follows to obtain a concrete building material [ ⁇ -8] for evaluation. That is, the area is the same as the area of the uncured panel laminate, preheated to 130 ° C. in advance, and the engraved iron plate is placed on the curable resin composition layer [II-1] side of the panel laminate, Further, by applying a load of 50 kgf / cm 2 and leaving it in a constant temperature bath at 130 ° C. for 60 minutes to cure the curable resin composition layers [I-1] and [II-1], A concrete building material [ ⁇ -8] was obtained. The surface of the iron plate is engraved in a staggered pattern with squares having a depth of 100 ⁇ m and a side of 5 mm arranged at equal intervals.
  • polyester film [III] of the concrete building material [ ⁇ -8] obtained above is peeled off and sprayed with a commercially available acrylic lacquer on this surface twice, it is rich in gloss and has a staggered lattice. A surface having an uneven design was obtained.
  • two straight cuts with a cutter knife are put on the cured film surface in a crossed shape, and a commercially available gum tape is pasted so as to cover the intersection of the cuts, and a roll of 5 kg is reciprocated 10 times. And completely bonded.
  • this gummed tape was peeled from the end portion at a constant speed of 10 m / min, no peeling of the cured film was observed at the cut portion.
  • the concrete building material [ ⁇ -8] was fixed in the air with the surface on which the cured film was not laminated facing up, and the center of the panel surface was struck 5 times with bare hands. Debris etc. were not removed from the surface side.
  • this concrete building material [ ⁇ -8] is cut with an electric saw equipped with a lightweight cellular concrete blade so that the cut end is perpendicular to the bonding surface of the concrete building material [ ⁇ -8], Further, the cross section was polished with # 40 sandpaper, followed by # 400 sandpaper, and the concrete panel surface and the curable resin composition layers [I-1] and [II-1] laminated thereon were formed. The boundary was clearly observable with a magnifying glass, and the thickness from the average line of the boundary to the surface of the curable resin composition layer [II-1] was measured. The thickness of the thin part was 144 ⁇ m.
  • Example 9 A laminate in which the curable resin composition layer [I-1] of the laminated film (IV-1) and the curable resin composition layer [II-1] of the laminated film (IV-4) are laminated and heated to 100 ° C.
  • the concrete surface coating layer of the present invention shown in FIG. 2 is bonded with a roll at a speed of 1 m / min, the polyester film [III] on the curable resin composition layer [I-1] side of this laminate is peeled off.
  • a laminated film (IV-6) for forming a concrete surface coating layer according to the laminated film (20) for formation was prepared.
  • Example 5 the surface on the outer wall side of the concrete panel was brought into contact with the curable resin composition layer [I-1] of the laminated film (IV-6) for forming the concrete surface coating layer to cover the concrete surface.
  • a laminated film for layer formation (IV-6) was laminated and laminated at a rate of 0.25 m / min while pressing it with a rubber roll heated to 150 ° C. at a linear pressure of 2 kg / cm to obtain an uncured panel laminate. Obtained.
  • the panel laminate is placed on an iron plate having the same area as the obtained panel laminate and a smooth surface, with the surface on which the laminated film is laminated facing down, and in this state, 130 ° C.
  • the curable resin composition layers [I-1] and [II-1] were cured by placing them in a constant temperature bath heated to 1 hour to obtain a concrete building material [ ⁇ -9] for evaluation. .
  • the surface of the cured film side of the concrete building material [ ⁇ -9] obtained above is smooth, the polyester film [III] is peeled off, and a commercially available acrylic lacquer is applied to the surface by spray coating twice. A flat design surface rich in gloss was obtained.
  • two straight cuts with a cutter knife are put on the cured film surface in a crossed shape, and a commercially available gum tape is pasted so as to cover the intersection of the cuts, and a roll of 5 kg is reciprocated 10 times. And completely bonded. When this gummed tape was peeled from the end portion at a constant speed of 10 m / min, no peeling of the cured film was observed at the cut portion.
  • this concrete building material [ ⁇ -9] is cut with an electric saw equipped with a lightweight foam concrete blade so that the cut end is perpendicular to the bonding surface of the concrete building material [ ⁇ -9], Further, the cross section was polished with # 40 sandpaper, followed by # 400 sandpaper, and the concrete panel surface and the curable resin composition layers [I-1] and [II-1] laminated thereon were formed. The boundary was clearly confirmed with a magnifying glass, and the thickness from the average line of the boundary to the surface of the curable resin composition layer [II-1] was measured and found to be 348 ⁇ m.
  • Example 10 Using the laminated films (IV-1) and (IV-4), a concrete building material for evaluation [ ⁇ -10] was obtained using the laminated films (IV-1) and (IV-4) in the same manner as in Example 9, except that the concrete panel whose surface was polished was used. It was. Specifically, after drying for 24 hours at 80 ° C., the surface on the outer wall side of the concrete panel (“Hebel Power Board Flat Panel” (thickness 37 mm) manufactured by Asahi Kasei Construction Materials Co., Ltd.) (P), cooled to room temperature, Using a grinder equipped with # 40 sandpaper, it was uniformly polished and cut to a depth of 3 mm to expose more foamed bubbles than the surface before polishing. This new surface was laminated so that the curable resin composition layer [I-1] surface side of the laminated film (IV-1) overlaps, and thereafter, the concrete building material for evaluation [ ⁇ - 10].
  • the curable resin composition layer [I-1] surface side of the laminated film (IV-1) overlaps, and thereafter
  • the surface of the cured film side of the concrete building material [ ⁇ -10] obtained above is smooth, the polyester film [III] is peeled off, and a commercially available acrylic lacquer is applied to the surface by spray coating twice. A flat design surface rich in gloss was obtained.
  • two straight cuts with a cutter knife are put on the cured film surface in a crossed shape, and a commercially available gum tape is pasted so as to cover the intersection of the cuts, and a roll of 5 kg is reciprocated 10 times. And completely bonded. When this gummed tape was peeled from the end portion at a constant speed of 10 m / min, no peeling of the cured film was observed at the cut portion.
  • the concrete building material [ ⁇ -10] is cut with an electric saw equipped with a lightweight foam concrete blade so that the cut end is perpendicular to the bonding surface of the concrete building material [ ⁇ -10], Further, the cross section was polished with # 40 sandpaper, followed by # 400 sandpaper, and the concrete panel surface and the curable resin composition layers [I-1] and [II-1] laminated thereon were formed. The boundary was clearly confirmed with a magnifying glass, and the thickness from the boundary to the surface of the curable resin composition layer [II-1] was measured to be 229 ⁇ m.
  • Example 11 In the same manner as in Example 5, a concrete building material [ ⁇ -11] for evaluation was obtained using the laminated films (IV-1) and (IV-5). Specifically, after being dried at 80 ° C. for 24 hours, the concrete panel (“Hebel Power Board Flat Panel” manufactured by Asahi Kasei Construction Materials Co., Ltd. (thickness 37 mm)) (P) laminated to the surface on the outer wall side is cooled to room temperature.
  • the film (IV-1) was laminated in the same manner as in Example 5 so that the curable resin composition layer [I-1] surface side of the film (IV-1) was overlapped. [III] was peeled off. On the curable resin composition layer [I-1], the laminated film (IV-5) was further laminated so that the curable resin composition layer [II-2] surface side overlapped.
  • a concrete building material [ ⁇ -11] for evaluation was obtained.
  • the concrete building material [ ⁇ -11] was fixed in the air with the surface side where the cured film was not laminated facing up, and the panel surface center was struck 5 times with bare hands. Debris etc. were not removed from the surface side.
  • this concrete building material [ ⁇ -11] is cut with an electric saw equipped with a lightweight foam concrete blade so that the cut end is perpendicular to the bonding surface of the concrete building material [ ⁇ -11], Further, the cross section was polished with # 40 sandpaper and subsequently with # 400 sandpaper, and the concrete panel surface and the curable resin composition layers [I-1] and [II-2] laminated thereon were formed. The boundary was clearly confirmed with a magnifying glass, and the thickness from the average line of the boundary to the surface of the curable resin composition layer [II-2] was measured and found to be 428 ⁇ m.
  • Example 6 Two curable resin composition layers [I] were used in the same manner except that another laminated film (IV-1) was used instead of the concrete surface coating layer-forming laminated film (IV-4). -1] and [I-1] were obtained as a concrete building material [ ⁇ -12].
  • the concrete building material [ ⁇ -12] was fixed in the air with the surface side where the cured film was not laminated facing up, and the panel surface center was struck 5 times with bare hands. Debris etc. were not removed from the surface side.
  • this concrete building material [ ⁇ -12] is cut with an electric saw equipped with a lightweight foam concrete blade so that the cut end is perpendicular to the bonding surface of the concrete building material [ ⁇ -12], Further, the cross section was polished with # 40 sandpaper, followed by # 400 sandpaper, and the concrete panel surface and the curable resin composition layers [I-1] and [I-1] laminated thereon were formed. The boundary was clearly confirmed with a magnifying glass, and the thickness from the average line of the boundary to the surface of one of the curable resin composition layers [I-1] was measured and found to be 66 ⁇ m.
  • Example 6 In Example 6, two curable resin composition layers [I-] were used in the same manner except that another laminated film (IV-1) was used instead of the concrete surface coating layer-forming laminated film (IV-4). An uncured panel laminate having 1] and [I-1] was obtained. The same area as this uncured panel laminate, preheated to 130 ° C. in advance, and the engraved iron plate is placed on the curable resin composition layer [I-1] side of the panel laminate, By applying a load of 50 kgf / cm 2 and leaving it in a constant temperature bath at 130 ° C. for 60 minutes to cure the curable resin composition layers [I-1] and [I-1], Concrete building material [ ⁇ -13] was obtained. The surface of the iron plate is engraved in a staggered pattern with squares having a depth of 100 ⁇ m and a side of 5 mm arranged at equal intervals.
  • polyester film [III] of the concrete building material [ ⁇ -13] obtained above is peeled off and sprayed with a commercially available acrylic lacquer on this surface twice, it has a houndstooth design. A surface was obtained. However, in the houndstooth check pattern, the unevenness of the bubbles exposed by the lightweight cellular concrete was reflected in the thin resin part.
  • two straight cuts with a cutter knife are put on the cured film surface in a crossed shape, and a commercially available gum tape is pasted so as to cover the intersection of the cuts, and a roll of 5 kg is reciprocated 10 times. And completely bonded. When this gummed tape was peeled from the end portion at a constant speed of 10 m / min, no peeling of the cured film was observed at the cut portion.
  • the concrete building material [ ⁇ -13] was fixed in the air with the surface on which the cured film was not laminated facing up, and the panel surface center was struck 5 times with bare hands. Debris etc. were not removed from the surface side.
  • the concrete building material [ ⁇ -13] is cut with an electric saw equipped with a lightweight foam concrete blade so that the cut end is perpendicular to the bonding surface of the concrete building material [ ⁇ -13].
  • the cross section was polished with # 40 sandpaper, followed by # 400 sandpaper, and the concrete panel surface and the curable resin composition layers [I-1] and [I-1] laminated thereon were formed.
  • the boundary was clearly confirmed by a magnifying glass, and the thickness from the average line of the boundary to the surface of one of the curable resin composition layers [I-1] was measured. It was 5 ⁇ m or less (measurement impossible) at the thin part of the lattice.
  • an ALC having a square shape with a side of 30 cm is prepared, and an inverted conical recess having a surface opening diameter of 1 mm and a depth of 1 mm is provided on the ALC surface.
  • a test base material was prepared by forming 5 pieces in the vertical direction and 5 pieces in the horizontal direction, with a space of 5 cm each, for a total of 25 pieces. Except that the concrete panels used in Examples 5, 9, 11, and 12 were changed to the above-mentioned test base materials, the laminated films were pasted and cured in the same manner as the methods described in the respective examples. The filling property of the resin into 25 concave portions having gaps was visually evaluated.
  • the evaluation criteria are as follows.
  • Example 5 was “ ⁇ ”
  • Example 9 was “ ⁇ ”
  • Example 11 was “ ⁇ ”
  • Example 12 was “x”.
  • the laminated film for forming a concrete surface coating layer of the present invention can be bonded to concrete such as lightweight cellular concrete (ALC) and cured to form a coating layer on the concrete surface.
  • the laminated film has good workability and productivity.
  • multilayer film of this invention is bonded and the concrete panel surface hardened becomes smooth and is excellent in surface smoothness, it is excellent also in design formability.
  • the laminated film of the present invention can be brought into close contact with the concrete surface, it is excellent in the protection of the concrete surface.
  • the laminated film for forming a concrete surface coating layer of the present invention can be used to increase the degree of freedom in design of the surface of concrete such as lightweight cellular concrete (ALC) used as an outer wall of a building.
  • ALC lightweight cellular concrete
  • the complicated painting process at the time of construction can be replaced with a process in a lightweight aerated concrete (ALC) factory, and can be used to realize simplification of on-site work.
  • ALC lightweight aerated concrete
  • it can be used to reduce contamination and breakage during transportation and storage of lightweight cellular concrete (ALC).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

La présente invention concerne un film stratifié pour former une couche de revêtement d'une surface en béton, présentant d'excellentes propriétés de protection pour protéger la surface en béton contre les dommages, et un excellent lissé de surface pour lisser la surface en béton et améliorer les propriétés de conception. Ce film stratifié (10) pour former une couche de revêtement d'une surface en béton est caractérisé en ce qu'il est obtenu par stratification d'une couche (1) comprenant une composition de résine durcissable et d'un film support (2).
PCT/JP2015/064230 2014-05-21 2015-05-18 Film stratifié pour former une couche de revêtement d'une surface en béton, matériau de construction en béton et son procédé de production WO2015178353A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201580025922.0A CN106458774B (zh) 2014-05-21 2015-05-18 混凝土表面覆盖层形成用层叠薄膜、混凝土制建筑材料和其制造方法
EP15795752.3A EP3147271B1 (fr) 2014-05-21 2015-05-18 Film stratifié pour former une couche de revêtement d'une surface en béton, matériau de construction en béton et son procédé de production

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JP2014105265 2014-05-21
JP2014-105265 2014-05-21
JP2014195899 2014-09-25
JP2014-195899 2014-09-25
JP2015042320A JP6565222B2 (ja) 2014-09-25 2015-03-04 コンクリート表面被覆用積層フィルム及びコンクリート表面被覆方法
JP2015-042320 2015-03-04

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018130720A1 (fr) 2017-01-16 2018-07-19 Lohmann Gmbh & Co. Kg Revêtement de sol, de mur et de plafond
US11168193B2 (en) 2018-07-30 2021-11-09 3M Innovative Properties Company Foams and methods of making

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JPS6264544A (ja) * 1985-06-28 1987-03-23 エクソン　ケミカル　パテンツ　インコ−ポレ−テツド 複合材料の改良製法
JPH0494931A (ja) * 1990-08-10 1992-03-27 Dainippon Printing Co Ltd 化粧シート及び該化粧シートを用いた化粧方法
JP2000127328A (ja) * 1998-10-22 2000-05-09 Kotobuki Seihan Printing Co Ltd 化粧シートおよびこの化粧シートの製造方法
JP2007268937A (ja) * 2006-03-31 2007-10-18 Dainippon Printing Co Ltd 発泡壁紙
JP2009291967A (ja) * 2008-06-03 2009-12-17 Aica Kogyo Co Ltd 化粧板および化粧板の製造方法

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Publication number Priority date Publication date Assignee Title
JPS6264544A (ja) * 1985-06-28 1987-03-23 エクソン　ケミカル　パテンツ　インコ−ポレ−テツド 複合材料の改良製法
JPH0494931A (ja) * 1990-08-10 1992-03-27 Dainippon Printing Co Ltd 化粧シート及び該化粧シートを用いた化粧方法
JP2000127328A (ja) * 1998-10-22 2000-05-09 Kotobuki Seihan Printing Co Ltd 化粧シートおよびこの化粧シートの製造方法
JP2007268937A (ja) * 2006-03-31 2007-10-18 Dainippon Printing Co Ltd 発泡壁紙
JP2009291967A (ja) * 2008-06-03 2009-12-17 Aica Kogyo Co Ltd 化粧板および化粧板の製造方法

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Title
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018130720A1 (fr) 2017-01-16 2018-07-19 Lohmann Gmbh & Co. Kg Revêtement de sol, de mur et de plafond
DE102017100759A1 (de) 2017-01-16 2018-07-19 Logis AG Boden-, Wand- und Deckenverkleidung
US11168193B2 (en) 2018-07-30 2021-11-09 3M Innovative Properties Company Foams and methods of making

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