KR100216783B1 - Formation of composite film and composite coating structure - Google Patents

Abstract

The present invention provides a method of forming a composite coating structure in which a coating film excellent in water resistance, acid resistance, alkali resistance and mechanical strength is combined with concrete, cement mortar, asphalt or metal and a composite coating structure having the composite coating. According to the present invention, a coating film (A) made of a polyolefin resin is formed by spraying, a primer made of a urethane resin is coated on the coating film (A) to form a coating film (B) And forming a layer (D) by applying at least one selected from the group consisting of cement mortar, cement concrete and packaging asphalt onto the coating (C).

Description

METHOD OF FORMING MULTI-COATED FILM

TECHNICAL FIELD The present invention relates to a method for forming a composite coating and a composite coating structure, and more particularly to a method for forming a composite coating structure in which a coating film excellent in water resistance, acid resistance, alkali resistance and mechanical strength is integrated with concrete, cement mortar, asphalt or metal, And a composite coating structure having a coating.

Conventionally, various protective films are formed on the surfaces of steel cement products or steel structures made of concrete, cement mortar, etc. constituting the concrete structure floor, wall, ceiling, etc. for the purpose of waterproofing, Has been done. In addition, mortar also forms outer walls after waterproofing with a waterproof sheet or the like for exterior waterproofing of building exterior walls and the like.

Various materials are used to form the protective film. For example, reactive curing resins such as epoxy resins, urethane resins, and vinyl ester resins have been widely used as the anticorrosive materials. Examples of waterproof materials include epoxy resins, urethane resins, unsaturated polyester resins, vinyl ester resins and the like A reactive curing resin or an asphalt emulsion or a rubber-modified asphalt emulsion. In addition, a method and structure for forming a waterproof layer by superimposing or adhering sheets such as polyethylene, soft polyvinyl chloride, ethylene-vinyl acetate copolymerized polymer, synthetic rubber or the like as a sheet waterproof material or by heating and melting asphalt are also made.

However, depending on the conventional waterproofing material, method material or method, the performance required for the coating may not be sufficiently satisfied. For example, it is very difficult to form a film on the surface of a concrete structure or a steel structure, and then integrally form concrete or asphalt on the film. Further, even if concrete or asphalt can be formed on the film, the adhesiveness with the film is low and the performance of the film itself can not satisfy the demand. In addition, although the coating made of an epoxy resin material can be integrated with concrete or asphalt, since this epoxy resin coating film lacks the elongation property of the material against the crack generated in the structure, cracks are generated, There is a concern that it can not be exercised. Therefore, it is possible to consider the case of using an epoxy resin-based or urethane resin-based material in which a stretch property is imparted to a material. However, the film made of such a material generally has a problem of low mechanical strength. Further, the asphalt material or the sheet waterproofing material has a problem that adhesion to concrete, asphalt or metal is very low. In addition, the sheet waterproofing material tends to have defects in the sheet joining portion, thereby deteriorating the waterproof function.

Accordingly, it is a first object of the present invention to provide a method for forming a composite coating capable of integrally forming a layer made of cement concrete, cement mortar or asphalt on a film excellent in water resistance, acid resistance, alkali resistance and mechanical strength .

A second object of the present invention is to provide a method for forming a composite coating film having excellent waterproofness, acid resistance, alkali resistance and mechanical strength on the surface of a structure.

A third object of the present invention is to provide a composite coating structure coated with a composite having the above excellent properties.

In order to solve the above problems, the present invention is characterized in that a coating film (A) made of a polyolefin resin is formed by spraying as a first embodiment, a primer made of a urethane resin is coated on the coating film (A) (D) is formed by placing at least one selected from the group consisting of cement mortar, cement concrete, and packaging asphalt on the coating (C), applying the epoxy resin onto the coating (B) And a process for forming a composite coating film.

In the second embodiment of the present invention, a coating film (A) made of a polyolefin resin is formed on the surface of a structure (E) by a spray method and a primer made of urethane resin is applied on the coating film (A) (D) is formed by placing at least one selected from the group consisting of cement mortar, cement concrete, and packaging asphalt on the coating (C), applying the epoxy resin onto the coating (B) And a process for forming a composite coating film.

In a third embodiment of the present invention, a coating film (F) is formed by applying at least one primer selected from an epoxy resin and a urethane resin to the surface of the structure (E) , Coating a primer made of a urethane resin on the coating (A) to form a coating (B), coating the coating (B) with an epoxy resin to form a coating (C) And forming a layer (D) by placing at least one selected from the group consisting of cement mortar, cement concrete, and asphalt for packaging on the substrate (C).

As a fourth mode of the present invention, a coating film (A) made of a polyurea resin is formed by a spray method, and one kind of primer selected from a urethane resin and a vinyl resin is applied onto the coating (A) And a step of forming a coating film (A) comprising a polyolefin resin on the coating film (G) by spraying.

The present invention relates to a composite body comprising the composite coating film of the first aspect, which comprises a coating (A) comprising a polyolefin resin on its surface, a coating (B) comprising a urethane resin on the coating (A) And a layer (D) formed of at least one selected from cement mortar, cement concrete, and packaging asphalt formed on the coating (C) formed of the epoxy resin formed on the substrate (C).

The present invention relates to a structure including the coating film of the second embodiment, which comprises a coating (A) comprising a polyolefin resin on the surface, a coating (B) comprising a urethane resin on the coating (A) There is provided a composite coating structure comprising a coating (C) formed of an epoxy resin formed and at least one selected from cement mortar, cement concrete and asphalt for packaging formed on the coating (C).

Further, the present invention is a structure including the composite coating film of the third aspect, wherein a coating film (F) composed of at least one selected from an epoxy resin and a urethane resin and a polyolefin resin formed on the coating film (F) A coating film (B) made of a urethane resin formed on the coating (A), a coating (C) made of an epoxy resin formed on the coating (B), a cement mortar formed on the coating (C) Cement concrete and asphalt for packaging, thereby providing a composite coating structure comprising layer (D).

The present invention also provides a structure comprising the coating film of the fourth aspect, wherein the coating film (A) comprises a polyolefin resin on the surface, and at least one primer selected from a urethane resin and a vinyl resin formed on the coating (A) And a coating film (A) comprising a polyolefin resin formed on the coating film (G).

Hereinafter, the method of forming a composite coating film according to the present invention (hereinafter referred to as [the method of the present invention]) and the composite coating film structure (hereinafter referred to as [the present invention structural body]) will be described in detail.

The method of the present invention basically comprises a step of forming a coating (A) made of a polyolefin resin on the surface of a structure, and a method of forming a composite coating comprising the coating (A) as an essential component.

The strength of the coating film (A) was determined to have a tensile strength of 9.8 MPa or more and a tensile strength of 10.8 MPa or more in order to support the resistance to the shear force applied to the structure, Or more. Particularly, in the case of a concrete structure, Or more is preferable as the polyolefin elastomer.

In the present invention, the structure forming the film (A) is not particularly limited as long as it can form a film as a structure requiring a method, waterproofing, chemical resistance and the like. For example, it is possible to use an underground structure such as bridge elevation, bridge pier, bridge top, underground structure such as a building or a collective house, roof or outer wall of a tunnel, a bottom plate and inner wall or outer wall of a tunnel such as a subway or a road, Concrete such as a reservoir, a waterway, a water and sewage treatment tank, a fire wall, and a bridge, a cement agent made of cement mortar, polymer cement, or a steel or plastic structure.

Further, in the present invention, a method of forming a composite coating on the surface of a molded concrete product using a mold panel for molding a concrete or the like according to the method of the present invention can be applied to a method of manufacturing a composite coating film, It is suitably used for the formation of structures such as structures and outer walls, inner walls and outer walls of subways and roads, upper resin, drainage pipes, waterways, water supply and drainage tanks, In the case of using this mold panel, in the step of forming the film A without adhering it, the surface of the mold panel may be formed by applying a releasing agent such as silicone or fluorine compound, or attaching a film having good releasability such as polyethylene or polypropylene It is preferable to perform processing.

In the step of forming the film (A) on the surface of the structure in the method of the present invention, a primer made of at least one resin selected from an epoxy resin and a urethane resin is applied prior to the formation of the film (A) It is preferable that the surface of the structure is reinforced and the adhesion between the structure and the film (A) can be enhanced. Particularly, it is preferable when the coating film (A) is formed on the surface of a structure such as a cement agent or a steel structure. An epoxy resin, and a urethane resin with an organic solvent type epoxy resin-based primer, an organic solvent-based urethane resin-based primer, and an emulsion type epoxy primer.

The epoxy resin used as a primer is a composition comprising a resin consisting of a resin having at least two epoxy groups in one molecule, a reactive diluent having at least one epoxy group in one molecule, and a modifier, if necessary, .

Examples of the resin having two or more epoxy groups in a molecule include condensation products of bisphenols such as bisphenol A, bistenol AD and bisphenol F with epichlorohydrin, novolak resins obtained from phenols and formalin, and epichlorohydrin , A condensation product of the condensation product and a polyethylene glycol chain having a molecular weight of 700 1,500 amines, and the like.

Examples of reactive diluents having one or more epoxy groups in one molecule include monoglycidyl ethers such as n-butyl glycidyl ether prepared from alcohols having 4 or more carbon atoms, 1,6-hexanediol diglycidyl Polyfunctional glycidyl ethers such as dicyclohexyl ether and dicyclohexyl ether, phenylglycidyl ethers prepared from phenols, and? -Glycidoxypropyltrimethoxysilane. These are preferably used for the purpose of imparting low viscosity and flexibility Lt; / RTI >

Examples of the modifier include a material for emulsifying a resin such as chroman, indine or dicyclopentadiene, a polyoxyalkylene amine composed of ethylene oxide and propylene oxide, and the like.

Examples of the curing agent include chain aliphatic polyamines such as polyethylene polyamine, polyoxyalkylene polyamine and polymethylenediamine, alicyclic polyamines such as menthylene diamine, norbornenediamine and isophorone diamine, and fatty aliphatic amines such as xylylenediamine , Monoglycidyl ethers such as n-butyl glycidyl ether prepared from polyamines and alcohols having 4 or more hydrogen atoms, polyfunctional glycidyl ethers such as 1,6-hexanediol diglycidyl ether, A derivative synthesized by an addition reaction with acrylonitrile or a derivative synthesized by an addition reaction with an epoxy resin such as diglycidyl ether produced by Bistenol or the like, And a derivative synthesized by a Mannich reaction from phenol or a derivative synthesized by a condensation reaction with a fatty acid The. These may be used alone or in combination of two or more.

Particularly, in view of the excellent workability in the coating operation for forming the coating film (F), it is preferable to use a resin having at least two epoxy groups in one molecule, a reactive diluent having at least one epoxy group in one molecule, A coating liquid prepared by diluting an epoxy resin composition containing a curing agent as a basic component with a solvent, a coating liquid prepared by dispersing an emulsifier in an epoxy resin composition and dispersed in water, or a coating liquid prepared by dispersing a bisphenol and an epichlorohydrin A self-emulsifiable resin containing an epoxy group in which a polyoxyalkyleneamine is added to the condensation product of drin, and a coating liquid in which water is mixed with a polyamine. As the epoxy group-containing self-emulsifiable resin, for example, 100 parts by weight of a condensation product of bisphenol and epichlorohydrin and having a molecular weight of 900 And 10 parts by weight of a polyoxyalkyleneamine having a molecular weight of 1,100. As the polyamines, when the concentration of water at the time of turbidity at the time of mixing with water is 10 80 Weight , Preferably 20 60 Weight Polyamines are useful.

In the present invention, the composition used as a primer for forming the coating film (F) is 70 Epoxy resin composition diluted with a solvent in the range below is suitable, and when the structure is a concrete product, an aqueous dispersion type epoxy resin is suitable.

The urethane resin used as a primer for forming the coating film (F) is obtained by reacting a polyisocyanate with a polyol having two or more hydroxy groups in a molecule. These are a moisture-curing one-component urethane resin containing an isocyanate residue as a prepolymer which is a reactant of at least one polyisocyanate and a polyol, or a prepolymer having at least one isocyanate group in a molecule, which is a reaction product of a polyisocyanate and a polyol, And is used as an organic solvent type primer composed of a mixed urethane resin.

Examples of polyisocyanates include isophorone diisocyanate, 1,6,11-undecane triisocyanate, xylylene diisocyanate, cyclohexane 1,4-diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,8 Diisocyanate-4-isocyanate tetramethylxylene diisocyanate, 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'- Isocyanate, tetramethyl xylylene diisocyanate, and tolylene diisocyanate. These may be used singly or in combination of two or more.

Examples of the polyol include polyether polyols such as polyethylene ether glycol, polypropylene ether glycol and polytetramethyl ether glycol, polyethylene adipate glycol, polyethylene propylene adipate glycol, polybutylene adipate glycol, polyhexamethylene adipate glycol Polyester polyols such as polycaprolactone glycol, acrylic polyols, glycols such as aliphatic, aromatic and hetero-alcohols having a low molecular weight as a chain extender, triols such as trimethylolpropane, amine alcohols such as ethanolamine, And polyols having a high OH value. These may be used singly or in combination of two or more.

In addition, an appropriate amount of catalyst is used in combination with the urethane resin to control the drying curing reaction. As the catalyst to be used, for example, at least one selected from tertiary amines such as triethylenediamine, triethylenamine, and tetramethylbutanediamine, and metal compounds such as dibutyltin dilaurate and tin oxide, is used.

In the present invention, the coating amount of the coating film (F) is 50 200 g / , Preferably 50 155 g / Respectively. When the base of the structure is made of concrete, it is preferable to coat the coating (F) in two or more layers in order to prevent defects such as pinholes. Further, the time from the application of the primer made of the epoxy resin and / or the urethane resin to the formation of the coating film A of the polyolefin resin is important for firmly adhering between the coating film F and the coating film A , And it is preferable to form the coating film (B) during a period of time until the coating film (F) is in a dry and cured state in which it is possible to feel a dried state by touching with a finger defined by JIS K5400. The epoxy resin and / or the urethane resin is not preferable since the reaction point with the polyurethane is insufficient after the curing is completed to cause problems in the integrity (adhesiveness).

In the present invention, the coating film (F) may contain, if necessary, zinc oxide, ultramarine, carbon black, cadmium red, cobalt green, cobalt violet, cobalt blue, chromium oxide green, titanium oxide, cyanogen blue, titanium yellow, Colored pigments such as alumina, kaolin, activated carbon, active white clay, glass balloons, glass beads, glass flakes, glass beads, , Glass powder, graphite, diatomaceous earth, acidic clay, silica, zirconia, aluminum hydroxide, slag, zeolite, talc, calcium carbonate, magnesium carbonate, titanium dioxide, dolomite, bentonite, mica, magnesia, montmorillonite, An extender pigment can be blended.

In the present invention, the coating film (F) is formed by applying an organic solvent type primer composed of at least one kind of resin selected from epoxy resin and urethane resin by using a brush, roller brush or the like or by spray coating Or the like, and drying and curing the composition.

The polyolefin resin for forming the coating film (A) of the composite coating film formed in the present invention is preferably a polyolefin resin for forming a coating film (A) of the composite coating film, which comprises the following components (1) and / or (2) And a second component composed of a polyolefin and a polyolefin.

(1) An amine-terminated polyester polyamine 100 having an amine group bonded to a secondary carbon atom with respect to 100 parts by weight of an amine end chain extender 500 parts by weight.

(2) Primary alcohol and / or secondary alcohol terminated polyether polyols 500 parts by weight and catalyst 0 3 parts by weight.

(3) Isocyanate prepolymer.

Examples of the amine terminal chain extender of (1) include 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl- Diaminobenzene, 1,3,5-triethyl-2,6-diaminobenzene, 3,3 ', 5,5' -tetraethyl-4,4'-diaminodiphenylmethane, N, Bis (t-butyl) ethylenediamine, di (methylthio) toluenediamine, and the like. These amine terminal chain extender can be used singly or in combination of two or more.

The amine-terminated polyether polyamine of (1) is present at the terminal of a polyether obtained by reacting a lower alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide or a mixture thereof with a suitable polymerization initiator, for example. Is reacted with ammonia to replace the amino group with a hydroxyl group. For example, by reaction with a reduced amino group of a hydroxy group bonded to the terminal secondary carbon of polypropylene glycol having ethylene glycol as a nucleus. Specific examples of the amine-terminated polyether polyamines include those having an average molecular weight of 200 A molecular weight of 400 obtained by reductive amination of a hydroxy group bonded to the terminal secondary carbon of a polypropylene triol having 4100 of diamine, trimethylol propane or glycerin as a nucleus 5500 triamine, etc. These may be used singly or in combination of two or more.

(2) Examples of polyether polyols having a primary alcohol and / or secondary alcohol terminal include ethylene glycol, propylene glycol, glycerin, hexanetriol, trimethylol propane, polyethylene ether glycol, polypropylene ether glycol, polytetra Polyether polyols such as polyethylene glycol, polypropylene glycol, polypropylene glycol, polypropylene glycol, methylene ether glycol, polyethylene adipate glycol, polyethylene propylene adipate glycol, polybutylene adipate glycol, polyhexamethylene adipate glycol and polycaprolactone glycol; , An epoxy polyol, a butadiene polyol, a polyester polyether polyol, a polycarbonate polyol, a vegetable oil, etc. These may be used singly or in combination of two or more kinds.

(3) The isocyanate prepolymer is a prepolymer having at least one isocyanate group as a reaction product of a polyisocyanate and an active hydrogen compound in one molecule. In addition, the isocyanate prepolymer may contain a polyisocyanate monomer that does not react with an active hydrogen compound. The active hydrogen compound is a polyol, a polyamine or a mixture thereof, but is not limited thereto. For example, a reaction product of a polyisocyanate and a polyol and / or an amine-terminated polyether, wherein the ratio of the hydroxyl group of the polyol to the isocyanate group of the polyisocyanate of 0.02 0.3, or 0.02 of the amino group of the amine-terminated polyether 0.3 or the sum of the hydroxyl group of the polyol and the amino group of the amine-terminated polyether is 0.02 0.3, < / RTI > 25 Has a viscosity of 6000 mPa2 or less, preferably 3000 mPa2 or less. Examples of the polyisocyanate and the polyol include those exemplified for the urethane resin used as the coating (F) component.

Examples of the polyisocyanate include isophorone diisocyanate (IPDI), 1,6,11-undecane triisocyanate, m-xylene diisocyanate (MXDI), 1,8-diisocyanate-4-isocyanate methyloctane, bis Diisocyanate (HDI), 4,4'-diphenylmethane diisocyanate (MDI), tetramethylxylene diisocyanate (TMXDI), 2 (4-isocyanatocyclohexyl) methane , 4-tolylene diisocyanate (TDI), norbornene diisocyanate, carbodiimide modified products thereof, biuret modified products, uretonimine modified products and the like. These may be used singly or in combination of two or more.

In the polyurea elastomer, when the first component is a polyamine, the reaction between the amine and the isocyanate is generally very fast, so that it is not necessary to use the catalyst. Since this reaction is very fast, it is necessary to select a high-speed mixing method with high efficiency and a reaction system having a reaction rate suitable for sprayability and film-forming property. These two components are not affected by moisture and moisture, And the resulting polyurea elastomer is strong and elastic, and has characteristics of excellent chemical resistance, heat resistance, and water resistance. In addition, when it is required to be used in an environment free from moisture or moisture and not exposed to high temperature and high humidity, and in particular, a high strength is not required and a low cost is required, a combination containing the first component (B) It is advantageous. When the first component and / or the second-alcohol-terminated polyether polyol (2) is contained in the first component, the content thereof is preferably in the range of 0 to 100 parts by weight based on 100 parts by weight of the amine- 500 parts by weight, preferably 10 parts by weight 300 parts by weight. If it exceeds 500 parts by weight, the elongation is improved but the strength is remarkably lowered. As a catalyst for accelerating the curing reaction of the polyurea elastomer, there may be used triethylenediamine, N, N, N ', N, - tertiary amines such as tetramethylhexamethylenediamine, metal compounds such as dibutyltin dilaurate and dibutyltin diacetate, and / or mixtures thereof.

In the process of the present invention, as the polyolefin resin used for forming the coating (A), amine-terminated polyethers described in U.S. Patent Nos. 4,379,729, 4,433,067 and 4,444,910, aromatic diamine chain extender, polyisocyanate and polyol May be a quasi-prepolymer remaining as a part of the isocyanate group prepared as the unreacted polyisocyanate, or a polyolefin elastomer produced using an aromatic polyisocyanate may be used.

In the present invention, conventionally known ultraviolet absorbers, radical supplements, coloring agents, extender pigments, plasticizers, flame retardant agents, additives and the like may be added to the film (A), if necessary.

Examples of the ultraviolet absorber include RUVA-93 (manufactured by Otsuka Chemical Co., Ltd., Chinuvin P, Chinuvin 144, Chinuvin 320 (manufactured by Chiba Kagi Co., Ltd.), HCB (Daouz), and Sumitomo 100 (Sumitomo Sagaku Co., Ltd.) .

Examples of the radical supplements include Cymasolve 622, Cymasolve 944, Irganox 1010, Irganox 245 (manufactured by Ciba Geigy).

Examples of the colorant include inorganic pigments such as zincation, ultramarine, carbon black, cadmium red, cobalt green, cobald violet, cobalt blue, chromium oxide green, titanium oxide, celian blue, titanium yellow, , Kanji yellow, phthalocyanine green, phthalocyanine blue, benzidine yellow, and rake red.

Examples of extender pigments include alumina, kaolin, activated carbon, activated clay, glass balloon, glass beads, glass flake, glass powder, graphite, diatomaceous earth, silica, zirconia, aluminum hydroxide, slag, zeolite, talc, calcium carbonate, magnesium carbonate , Titanium dioxide, dolomite, bentonite, mica, magnesia, montmorillonite, and barium sulfate. Examples of the plasticizer include dioctyl phthalate and dibutyl phthalate. Examples of the flame retardancy imparting agent include tris-dichloropropyl phosphate (manufactured by Oya Kagaku).

The compounding agent to be blended according to the needs of the present invention is contained in the first component or the second component for forming the polyolefin resin.

In the method of the present invention, the step of forming the coating film (A) by the spray method is not particularly limited as long as it is a method capable of spraying the polyolefin resin material. For example, in the case of forming a film composed of the polyurea elastomer composed of the first component and the second component, the first component and the second component are weighed by a proportioner Pressure regulation Is heated and supplied to the inside of the spray gun, collides directly inside the spray gun, and is sprayed on the surface of the structure or the like while reacting. In the case where the reaction rate is relatively slow in the case of containing the first component (2) component, mixing by a stirring mixer or static mixer may be performed before supplying to the spray gun.

In the method of the present invention, when a layer (D) composed of at least one kind selected from cement mortar, cement concrete and packaging asphalt is formed on the film (A), the urethane resin and the vinyl resin A coating film B is formed by applying an organic solvent type primer made of at least one kind of resin and a primer made of an epoxy resin is applied on the coating film B to form a coating film C and then a layer D is formed (A) and the layer (D) are directly adhered to each other because the adhesiveness between the cured coating (A) and the coating (B), the coating (C) Can be indirectly integrated through the coating (B) and the coating (C). Particularly, it is preferable that the coating (B) is formed by coating a primer made of a urethane resin in view of good adhesion with the polyurea resin.

Examples of the vinyl resin used as a primer in the formation of the coating film (B) include polyvinyl chloride, polyvinyl acetate, and copolymers thereof.

The urethane resin used for forming the film (B) is preferably a polyurethane prepolymer having (a) a polyurethane prepolymer having isocyanate moieties at the molecular terminals formed by reacting a primary alcohol and / or a secondary alcohol-terminated polyol with a polyisocyanate Liquid organic urethane resin composition or polyol which is cured by moisture containing a main component and (b) an organic solvent, a first component liquid composed of a catalyst and an organic solvent, and a second component liquid composed of a polyisocyanate and an organic solvent And a two-component urethane resin composition which is mixed at a predetermined ratio before use.

As the one-liquid organic solvent type urethane resin composition, a polyurethane prepolymer having an isocyanate residue as a reaction product of a polyether polyol and 4,4'-dimethylmethane diisocyanate in the presence of a dibutyl chiefly dilaurate catalyst is dissolved in an organic solvent .

As the two-component urethane resin composition, an acrylic polyol solution which is a reaction product of methyl acrylate, styrene and methacrylic acid 2-hydroxy, a solvent of polycaprolactone polyol or neopentyl glycol, adipic acid and isophthalic acid A polyester polyol solution as a reaction product and an addition product of trimethylol propane such as toluene diisocyanate, m-xylene diisocyanate, hexamethylene-1,6-diisocyanate, and a buret or isocyanate solution as a second component liquid And the like.

The organic solvent for the urethane resin is not particularly limited as long as it dissolves the urethane resin. For example, an organic solvent containing at least one selected from ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, and xylene is preferable because the urethane resin and the coating film (A) improve adhesion.

In the present invention, such primers made of urethane resin are used as organic solvent type primers in combination of two or more kinds of single species.

In the present invention, when a structure having a layer (D) selected from cement mortar, concrete or packing asphalt is produced on the coating (A) composed of a polyolefin elastomer, it is preferable to use a composition comprising at least one member selected from the above urethane resin and vinyl resin A primer made of an epoxy resin is applied to the upper layer to form a coating film C and a primer made of an epoxy resin is applied to the upper layer to form a coating film C And then the layer (D) made of cement mortar, concrete or packing asphalt is formed on the upper layer thereof, especially since adhesion between the respective layers formed becomes stronger.

In the present invention, the epoxy resin used as a primer in the formation of the coating film (C) includes an epoxy resin having at least one epoxy group in one molecule and an epoxy resin curing agent. The epoxy resin has an epoxy equivalent (g / epoxy group: the same hereinafter) of 165 Bisphenol A type epoxy resin, bisphenol AD type epoxy resin, bisphenol F type epoxy resin, epoxy equivalent of 170 250 novolak type epoxy resin, an epoxy equivalent of 160 350 phosphoric acid diglycidyl ester, an epoxy equivalent of 100 250 glycidyl amines may be used. Of these, 25 A bisphenol A type epoxy resin, a bisphenol AD type epoxy resin and a bisphenol F type epoxy resin are preferable.

The epoxy resin has a number of carbon atoms of 11 At least one epoxy resin having at least one epoxy group in a molecule such as glycidyl ether of 1,4-cyclohexanediol, 1,6-hexanediol diglycidyl ether and trimethylolpropane triglycidyl ether, For the purpose of viscosity adjustment or imparting flexibility.

Examples of the epoxy resin curing agent include chain aliphatic polyamines such as polyethylene polyamines, polyalkylene ether polyamines and polymethylene polyamines, cyclic aliphatic polyamines such as N-aminoethylpyrazine and isophoronediamine, fatty aromatic amines such as xylenediamine, Amide amines composed of the above-mentioned polyamines and fatty acids, polyamide amines composed of the aforementioned polyamines and dimer acids, and polyamines composed of at least one of the above-mentioned modified polyamines derived from the above polyamines are preferable because of room temperature curing ability. Particularly, the polyamide amine obtained by dehydration condensation of polyethylene polyamine and dimer acid is used in an amount of 20 Or more, preferably 50 Or more of the curing agent is preferable because the curing agent is excellent in adhesion between the coating film (B) and the layer (D).

In the present invention, conventionally known coloring agents, extender pigments, additives and the like may be added to the coating film (C) as required.

Examples of the colorant include at least one selected from the group consisting of zincification, ultramarine, carbon black, cadmium red, cobalt green, cobalt violet, cobalt blue, chromium oxide green, titanium oxide, celian blue, titanium yellow, Kanji yellow, phthalocyanine green, phthalocyanine blue, benzidine yellow, and rake red.

Examples of extender pigments include alumina, kaolin, activated carbon, activated clay, glass balloon, glass beads, glass flake, glass powder, graphite, diatomaceous earth, silica, zirconia, aluminum hydroxide, slag, zeolite, talc, calcium carbonate, magnesium carbonate , Titanium dioxide, dolomite, bentonite, mica, magnesia, montmorillonite, and barium sulfate. In the present invention, the primer made of this epoxy resin is used as a solvent-free primer, an organic solvent primer, or an aqueous primer.

The surface of the coating film (D) is subjected to a method of coating the primer made of an epoxy resin with an aggregate such as sand or silica in the case of forming the coating (C), or by dispersing these aggregates at the time of applying the epoxy resin primer, The adhesive area of cement mortar, cement concrete, packaging asphalt and the like can be increased, and at the same time, the adhesive strength can be improved by the fixing effect.

The coating amount of the coating film (C) is usually 100 500 g / , Preferably 150 300 g / Respectively.

The layer (D) made of cement mortar, concrete, and packaging asphalt is applied to protect the coating (A) from the availability of iron or fallen materials such as welding during construction in the case of cement mortar, , And for asphalt, for example, a bridge top plate or an overpass.

In the present invention, in the case of forming a coating film (A) made of a polyurea resin or a coating made of a polyurethane resin or the like on the coating film (A), when the polyurea resin or the polyurethane resin is simply overlaid, If it is within 3 hours, sufficient integrity can be exhibited between the two coatings. However, if the polyolefine resin coating is already coated with the polyurea resin film already hardened, the integral property becomes insufficient and there is a possibility of delamination. Thus, a primer made of at least one kind of resin selected from a urethane resin and a vinyl resin is applied on the lower layer coating (A) so that the coatings (A) made of the polyolefin resin are sufficiently adhered to each other, (A) made of a polyolefin resin may be formed.

Examples of the urethane resin or vinyl resin used as a primer for forming the coating film (G) include those used for forming the coating film (B). Particularly, as the vinyl resin, phthalic acid ester is added to 100 parts by weight of polyvinyl chloride resin 30 parts by weight It is preferable to dissolve the added resin in a mixed solvent of methyl isobutyl ketone, xylene and butyl acetate because the films (A) can be firmly adhered to each other.

The thickness of the coating film (G) is usually 10 100 , Preferably 20 50 Respectively.

In the present invention, in order to protect the coating film made of the polyurea resin or the film made of the polyurethane resin from the polyurea resin or the polyurethane film from the sunlight and to improve the weather resistance, A coating is applied to form a coating. As light-shielding paints to be used, oil-based paints, alkyd resin paints, unsaturated polyester resin paints, urethane resin paints, acrylic resin paints, vinyl resin paints and the like can be mentioned. Among them, appearance stability, adhesion to polyurethane resin , Vinyl resin paints and non-sulfur-modified urethane resin paints are preferable.

A powder such as aluminum, zinc, iron, stainless steel or the like, carbon black, chromium oxide green, titanium oxide, bengalas or the like having a particle diameter of 0.1 500 A powder or an ultraviolet absorber or the like is particularly preferable.

The coating amount of the light-shielding coating material for forming the coating film (C) is usually 100 300 g / , Preferably 150 250 g / Respectively.

In the present invention, a specific organic solvent type primer is applied to the coating film (A) made of a polyurea elastomer formed with or without adhesion to a structure or the like to form a coating film (B) or a coating film (G) It is possible to obtain a structure having excellent durability by firmly bonding and integrating the concrete or asphalt layer (D) to be laid later with the waterproof and anticorrosive coating (A) by applying the epoxy resin-based primer to form the coating (C). The coating film A is coated with the coating film A to form a coating film A on the coating film A when the coating film A is repacked to increase the thickness of the coating film A, To obtain a waterproof and anticorrosive coating film which is integrated with the coating film.

In a structure used in an environment in which a coating made of a polyurea resin or a polyurethane resin is exposed to sunlight, a coating film-forming resin coating material containing a light-shielding material is applied to form a coating film, whereby a coating film made of a polyolefin resin or a polyurethane resin Durability can be maintained in the long term.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples of the present invention. However, the present invention is not limited to Examples and Comparative Examples.

[Example 1]

300 300 60 Of concrete plate with a diamond cutter (100 100 60 ) Is roughened by sand blasting. Next, 10 parts by weight of methoxypoly (oxyethylene / oxypropylene) -2-propylamine (average molecular weight: 1000) was added to 100 parts by weight of a bisphenol A type epoxy resin (epoxy equivalent: 189 g / , 43 parts by weight of epoxy-modified m-XDA (active hydrogen equivalent: 95 g / eq) and solubility in water: 32 g / 100 g) and 143 parts by weight of ion- The mixed and prepared two-solution mixed emulsion primer is applied twice with a brush to form a film (F).

Thereafter, an amine-terminated polyether prepared by reductive amination of the polyol with respect to 100 parts by weight of an amine-terminated polyether triamine (average molecular weight: 5000, trade name: Zephamine T-5000) 66.7 parts by weight of diamine (average molecular weight: 2000, trade name: Jeffamine D-2000), 64.6 parts by weight of diethyltoluene diamine and 27.1 parts by weight of N, N'-diethylaminodiphenylmethane were added and stirred to be mixed. And 5 parts by weight of titanium oxide were mixed to prepare a first component liquid colored with a white color. Further, 66.7 parts by weight of polypropylene glycol (average molecular weight: 2000) was reacted with 100 parts by weight of carbodiimide-modified methylenediphenyl diisocyanate, and 0.1 part by weight of phthalocyanine blue was mixed therewith to prepare a second component liquid colored in blue do.

The polylactic acid elastomer stock solution consisting of the first component solution and the second component solution was supplied to a spray gun connected to a high-pressure supply device (H-2000: manufactured by GUSMER), sprayed on a test concrete plate, (A) is formed.

Next, a moisture-curing type urethane prepolymer composed of a urethane prepolymer obtained by reacting TDI with polypropylene glycol (average molecular weight: 2000) in the presence of dibutyltin dilaurate, toluene, methyl ethyl ketone and ethyl acetate on the surface of the film (A) Urethane foam (nonvolatile matter: 35 , NCO content: 3.5 ) To 200 g / To form a coating film (B). After drying, an epoxy resin consisting of bisphenol A type epoxy resin and 1,6-hexanediol diglycidyl ether (epoxy equivalent: 180, viscosity: 950 mPa S / 25 ) And polyamideamine (trade name: Versamide 140) were dissolved in 75 parts by weight of 75 And a curing agent consisting of 60 parts by weight of a mixed solution of isopropyl alcohol and toluene contained in the coating solution (B) To form a coating film (C).

Subsequently, in a part of the coating film C, Width 70 Height 60 Cement mortar (Portland cement: Fuyo-sand: water = 20 parts by weight: 40 parts by weight: 13 parts by weight) was placed in a mold while the contact portion with the coating film was sealed and cured for 7 days . After the curing, the mold is removed, and a specimen of the composite coating structure obtained by forming the cement mortar (D) on the coatings (A), (B) and (C) is obtained.

The adhesive strength between the coating (A) and the layer (D) is measured by a compression shear adhesion test. The test was carried out by setting up a specimen, fixing the concrete plate containing the coating (A) with a jig, placing a block (wood: 50) on the upper surface of the layer 60 70 ), And this is done in accordance with the method of JIS K6852.

A stainless steel plate 500 (surface treated with a fluorine-based compound) 500 4 ) Was prepared, and on the surface thereof, a thickness 1 (A) is formed. This coating was removed from the stainless steel plate to obtain a free coating (A), and the tensile strength of the coating (A) was measured in accordance with JIS K6310. The results are shown in Table 1. The properties of this film (A) alone are tested according to JISA6021 (roof coating film waterproofing material). The results are shown in Table 2.

[Example 2]

The polyurea elastomer of Example 1 was replaced with an alcohol-terminated polyether triol and an alcohol-terminated polyether diol having an average molecular weight of about the same as the amine-terminated polyether in the first component, respectively, , A test sample of a composite coating structure was obtained in the same manner as in Example 1 and the adhesive strength between the coating film (A) and the layer (D) was measured by a compression shear adhesion test.

As in Example 1, a single coating film (A) was prepared and its tensile strength was measured. The results are shown in Table 1.

[Example 3]

A composite coating structure was obtained in the same manner as in Example 1, except that the primer coat (F) was not formed on the surface of the test concrete sheet in Example 1, and a composite coating structure was obtained between the coating (A) Is measured. The results are shown in Table 1.

[Comparative Example 1]

As in Example 1, the coating (A) is formed on the surface of the test concrete plate. Subsequently, a mold frame was placed on a part of the film (A) as in Example 1, and a cement mortar was placed and cured directly to obtain a test piece on which a layer (D) was formed. ) And the layer (D) is measured. The results are shown in Table 1.

[Comparative Example 2]

As in Example 2, the coating film (A) is formed directly on the surface of the test concrete plate. Subsequently, as in Example 1, a mold was put on a part of the film (A), and a cement mortar was placed and cured directly to obtain a test piece on which a layer (D) was formed. A) and the layer (D) is measured. The results are shown in Table 1.

[Comparative Example 3]

An asphalt roofing sheet (tensile strength: 2.9 MPa, JIS A6013; commercially available product) was fused to a test concrete plate treated in the same manner as in Example 1 to form a film. Subsequently, a mold was put on a part of the coating film as in Example 1, and a cement mortar was placed and cured directly to obtain a test piece on which a layer (D) was formed. The coating film (A) was obtained in the same manner as in Example 1, And the layer (D) is measured. The results are shown in Table 1.

[Example 4]

Thickness of about 25 Using wooden plywood (inner dimensions: 800 1700 50 ). On the inner side of the wooden frame, as in Example 1, a thickness 1 of polyolefin elastomer (A) of the coating film. Subsequently, a coating film (B) made of a moisture-curing urethane was formed on the surface of the coating film, and a coating film (C) made of an epoxy resin and a polyamideamine film was formed on the coating film (B) Asphalt for surface layer packaging was applied to the composite coating consisting of the coatings (A), (B) and (C) And then pressed with a loader to harden it, and a thickness of about 70 Of the asphalt layer (D).

The obtained composite coating structure was cut out with a cutter for each wooden frame, and a dimension of 100 100 About 75 (Adhesive area 10,000 square millimeters). Next, the adhesive strength between the coating (A) and the layer (D) is measured through a compression shear adhesion test of the test piece. The results are shown in Table 3.

[Comparative Example 4]

As in Example 4, the thickness of the polyolefin elastomer (A) is formed. Subsequently, on the surface of the coating film (A), a coating film having a thickness of about 70 Surface layer packing asphalt is laid, pressed with a loader to harden, and a thickness of about 50 Of the asphalt layer (D). The composite coating structure thus obtained was subjected to a compression shear adhesion test as in Example 4 to measure the adhesive strength between the coating (A) and the layer (D). The results are shown in Table 3.

[Example 5]

The cement mortar plate (70), in which the surface roughness was polished with a wire brush 70 20 (Manufactured by Nippon Test Panel Co., Ltd.), the coating film (F) and the coating film (A) are formed as in Example 1.

The adhesiveness of the obtained film (A) was evaluated by the following test piece 1 5 is prepared and examined.

(Test piece 1) After 2 hours from the preparation of the coating (A), one side (40) of the coating (A) Of the thickness of 50 (Manufactured by Toray Co., Ltd.), and then the coating film (A) was coated on the entire surface with 1 .

(Test piece 2) For one test piece, after three days from the preparation of the coating (A), one side 40 (A) was coated on the entire surface with a polyester film .

(Test piece 3) One of the other test pieces was coated with one side 40 of this film (A) after 3 days from the preparation of the film (A) And a moisture-curing urethane primer was applied onto the surface of the other part of the coating film (A) in a manner similar to Example 1 at 200 g / (B) is formed in a state in which it can be felt in a dry state by touching with a finger, and then the film (A) .

(Test piece 4) One of the other test pieces was coated with a polyester film as in Test piece 1 three days after the preparation of the film (A), and the polycaprolactone flurol was dissolved in toluene, ethyl acetate , A polyester polyol dissolved in a mixed solvent of butyl acetate and xylene, and an ethyl acetate solution (non-volatile matter: 75%) of a reaction product having a terminal isocyanate residue formed by reacting toluene diisocyanate with trimethylolpropane ), And a coating film (B) was formed in such a state that the coating film (B) was felt in a dry state by touching with a finger, and then the coating film (A) .

(Test piece 5) One of the other test pieces was covered with a polyester film like the test piece 1 three days after the preparation of the film (A), and 100 parts by weight of polyvinyl chloride resin was coated on the surface of the remaining part of the film (A) (B) was formed in such a manner that the film (A) could be felt in a dry state by touching with a finger, and then the film (A) .

Next, test piece 1 5 was allowed to stand for 3 days and cured. Then, the polyester film was removed from the film formed on the upper layer, (A), and the other side 30 And a coating film of the upper and lower coating films (A) adhered to each other. This test piece 1 The first layer coating A and the cement mortar were fixed with the other jig to be attached and the upper and lower coating layers A were fixed to each other with a tester Tensilon: manufactured by Toyo Baldwin Co., Ltd.) to evaluate the bonding state using a 180-degree peel test. Table 4 shows the results of evaluation based on the criteria shown in Table 3 below.

[Example 6]

The cement mortar plate (70), in which the surface roughness was polished with a wire brush 70 20 , Manufactured by Nippon Denshoku Kasei Kogyo Co., Ltd., manufactured by Nippon Kasei Kogyo Co., Ltd.) was used as the polyurethane elastomer material in the same manner as in Example 2, 5 are prepared, and the adhesion state of the upper and lower coating films A is evaluated. The results are shown in Table 4.

[Example 7]

The cement mortar plate (150), in which the surface roughness was polished with a wire brush 70 20 (Manufactured by NIPPON TEST PANEL CO., LTD.), An epoxy resin composed of bisphenol A type epoxy and 1,6-hexanediol diglycidyl ether (epoxy equivalent: 180, viscosity: 950 mPa S / 25 ), 50 parts by weight of modified polyamide amine , 130 parts by weight of an aqueous solution (trade name: Ancamide 360), 90 parts by weight of isopropyl alcohol and 30 parts by weight of ion-exchanged water is applied to form a film (F). Thereafter, on this coating film F again, as in Example 1, the thickness 2 To form a coating (A), and a concrete plate is applied to obtain a test sample for alkali resistance test and acid resistance test.

This specimen was cured for 3 days to give 10 Sulfuric acid aqueous solution and saturated calcium hydroxide aqueous solution for 60 days to measure the adhesive strength. The adhesive strength was 40 40 , The film A around the jig is cut off by a motorized cutter, and then measured using a dry type adhesion tester. The results are shown in Table 5.

[Example 8]

The stainless steel plate 500 (500 500 4 ) Having a thickness of 2 < RTI ID = 0.0 > (A) is formed. The coating film (A) was removed from the stainless steel plate to give a glass coating film (A) 70 . The same moisture-curing urethane primer as in Example 1 was coated on the surface of the cut film (A) at 200 g / To form a coating film (B), and then the two-liquid mixed type epoxy was fed at a rate of 200 g / After the coating C is formed by coating, the coating A is coated with a frame (inner dimension 150 70 Height 25 The coated film A is placed in the mold with the primer-treated side facing up. The cement mortar is put on the film (A) and cured for 21 days to form a composite coated structure.

The obtained composite coating structure is subjected to an adhesion test, an acid resistance test and an alkali resistance test in accordance with the test method of concrete method guide (draft) (June, 1993: Japan Sewerage Project Fragment). The results are shown in Table 6.

The adhesion test and the alkali resistance test are carried out using the composite coating structure itself as a test body.

The acid resistance test was conducted by polishing the side surface of the composite coating structure and the cement mortar surface to adjust the base, The above moisture-curing urethane primer was added in an amount of 20 g / After coating, the coating film (A) was coated on the primer coated portion at 2 To form a test body.

For reference, the moisture-curing urethane primer and the thickness 2 And a water permeability test is carried out. The results are shown in Table 6.

According to the coating film forming method of the present invention, a composite coating film excellent in adhesiveness, acid resistance, alkali resistance and water permeability can be obtained. Particularly, it is possible to obtain a structural body having excellent durability because a coating made of a strong polyolefin resin having a waterproof property and waterproof property, a concrete laid thereon, a packing asphalt, and the like can be firmly adhered.

Further, the composite coating structure of the present invention is useful because it has the above-described composite coating film having excellent properties.

Claims (14)

A coating film (A) made of a polyolefin resin is formed by a spray method and a primer made of a urethane resin is coated on the coating film (A) to form a coating film (B), and then an epoxy resin And forming a layer (D) by forming at least one selected from the group consisting of cement mortar, cement concrete and packing asphalt on the coating (C) Way. A coating film A made of polyolefin resin is formed on the surface of the structure E by a spray method and a primer made of a urethane resin is applied on the coating film A to form a coating film B, (D) by applying at least one selected from the group consisting of cement mortar, cement concrete and packing asphalt onto the coating (C) by applying an epoxy resin on the coating (C) To form a composite coating film. A coating film (A) made of a polyolefin resin is formed by a spray method after coating the surface of the structure (E) with at least one primer selected from an epoxy resin and a urethane resin to form a coating film (F) A primer made of a urethane resin is applied on the coating film A to form a coating film B and then an epoxy resin is applied on the coating film B to form a coating film C on which a cement mortar, A step of forming at least one selected from the group consisting of concrete and asphalt for packaging to form a layer (D). A coating film (A) made of a polyolefin resin is formed by a spray method, and at least one primer selected from a urethane resin and a vinyl resin is applied on the coating (A) to form a coating film (G) G), a coating film (A) comprising a polyolefin resin is formed by a spraying method. The polyolefin resin film (A) according to claim 1, wherein the polyolefin resin coating (A) is a combination of a first component composed of the following (1) and a second component composed of (3) A method for forming a composite coating film, comprising mixing two components out of a combination of a first component and a second component composed of (3) and reacting them. (1) an amine-terminated polyether polyamine 100 in which an amine group is bonded to a secondary carbon atom with respect to 100 parts by weight of an amine end chain extender 500 parts by weight (2) Primary alcohol and / or secondary alcohol-terminated polyether polyol 500 parts by weight and catalyst 0 3 parts by weight (3) isocyanate prepolymer. A coating film (A) comprising a polyolefin resin on the surface, a coating film (B) comprising a urethane resin on the coating film (A), a coating film (C) comprising an epoxy resin formed on the coating film (B) , A layer (D) made of at least one selected from cement mortar, cement concrete, and asphalt for packaging. (A) comprising a coating film (F) made of at least one selected from an epoxy resin and a urethane resin on the surface and a polyolefin resin formed on the coating film (F), and a urethane resin (D) formed of at least one selected from the group consisting of cement mortar, cement concrete and asphalt for packaging formed on the coating (C), a coating (C) formed of the epoxy resin formed on the coating (B) And a second coating layer formed on the second coating layer. A coating film (G) formed of a polyolefin resin on the surface and at least one primer selected from a urethane resin and a vinyl resin formed on the coating (A) A composite coating structure comprising a coating (A) made of a resin. The polyolefin resin film (A) according to claim 6, wherein the coating (A) comprises a combination of a first component consisting of the following (1) and a second component composed of (3) A composite coated structure characterized in that two kinds of components of the combination of the first component and the second component made of (3) are mixed and reacted. (1) an amine-terminated polyether polyamine 100 in which an amine group is bonded to a secondary carbon atom with respect to 100 parts by weight of an amine end chain extender 500 parts by weight (2) Primary alcohol and / or secondary alcohol-terminated polyether polyol 0 500 parts by weight and catalyst 0 3 parts by weight (3) isocyanate prepolymer. The polyolefin resin film (A) according to claim 2, wherein the polyolefin resin coating (A) is a combination of a first component consisting of the following (1) and a second component composed of (3) A method for forming a composite coating film, comprising mixing two components out of a combination of a first component and a second component composed of (3) and reacting them. (1) an amine-terminated polyether polyamine 100 in which an amine group is bonded to a secondary carbon atom with respect to 100 parts by weight of an amine end chain extender 500 parts by weight (2) Primary alcohol and / or secondary alcohol-terminated polyether polyol 0 500 parts by weight and catalyst 0 3 parts by weight (3) isocyanate prepolymer. The polyolefin resin coating (A) according to claim 3, wherein the coating (A) comprising the polyolefin resin is a combination of a first component consisting of the following (1) and a second component composed of (3) A method for forming a composite coating film, comprising mixing two components out of a combination of a first component and a second component composed of (3) and reacting them. (1) an amine-terminated polyether polyamine 100 in which an amine group is bonded to a secondary carbon atom with respect to 100 parts by weight of an amine end chain extender 500 parts by weight (2) Primary alcohol and / or secondary alcohol-terminated polyether polyol 0 500 parts by weight and catalyst 0 3 parts by weight (3) isocyanate prepolymer. The polyolefin resin film (A) according to claim 4, wherein the coating film (A) comprising the polyolefin resin is a combination of a first component consisting of the following (1) and a second component composed of (3) A method for forming a composite coating film, comprising mixing two components out of a combination of a first component and a second component composed of (3) and reacting them. (1) an amine-terminated polyether polyamine 100 in which an amine group is bonded to a secondary carbon atom with respect to 100 parts by weight of an amine end chain extender 500 parts by weight (2) Primary alcohol and / or secondary alcohol-terminated polyether polyol 0 500 parts by weight and catalyst 0 3 parts by weight (3) isocyanate prepolymer. The polyolefin resin film (A) according to claim 7, wherein the polyolefin resin coating (A) is a combination of a first component composed of the following (1) and a second component composed of (3) A composite coated structure characterized in that two kinds of components of the combination of the first component and the second component made of (3) are mixed and reacted. (1) an amine-terminated polyether polyamine 100 in which an amine group is bonded to a secondary carbon atom with respect to 100 parts by weight of an amine end chain extender 500 parts by weight (2) Primary alcohol and / or secondary alcohol-terminated polyether polyol 0 500 parts by weight and catalyst 0 3 parts by weight (3) isocyanate prepolymer. The polyolefin resin coating (A) according to claim 8, wherein the coating (A) comprises a combination of a first component consisting of the following (1) and a second component composed of (3) A composite coated structure characterized in that two kinds of components of the combination of the first component and the second component made of (3) are mixed and reacted. (1) an amine-terminated polyether polyamine 100 in which an amine group is bonded to a secondary carbon atom with respect to 100 parts by weight of an amine end chain extender 500 parts by weight (2) Primary alcohol and / or secondary alcohol-terminated polyether polyol 0 500 parts by weight and catalyst 0 3 parts by weight (3) isocyanate prepolymer.