JP2580829B2 - Composite covering structure, civil engineering building and composite covering structure construction method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a concrete and mortar structure, a crack-following material applied to a metal precursor, a waterproof property, a carbon dioxide gas barrier property, a salt barrier property, and a The present invention relates to a composite covering structure, a civil engineering building, and a method of constructing a composite covering structure that is excellent in integration with a body and blister resistance.

[Conventional technology]

As a waterproof coating film-type structure based on a concrete structure or a metal precursor, as described in JP-B-52-25877, a flexible unsaturated polyester resin and a fiber reinforcing material are combined. As described in JP-A-58-189071, a coated structure of a foamed polyurethane resin is known.

Japanese Patent Application Laid-Open No. 01-219242 proposes a construction method in which a polyurethane resin layer and an FRP layer are combined to improve crack followability, waterproofness, carbon dioxide gas barrier properties, salt barrier properties, and the like.

[Problems to be solved by the invention]

The above-described FRP structure is excellent in water resistance, heat resistance, salt barrier properties, abrasion resistance, weather resistance, gas barrier properties, and the like, depending on the performance of the resin used. However, there is a disadvantage that the elongation of the material is extremely small due to the inclusion of the fiber reinforcing material. This drawback causes the following problems.

That is, in buildings such as concrete and mortar, low-speed and high-speed expansion and contraction motions occur repeatedly due to drying shrinkage, land subsidence, earthquakes, and the like, so that cracks are inevitably generated on the surface. And since such cracks cause water leakage, it is necessary to waterproof these buildings. In general, when such waterproofing is performed, the applied waterproofing material is such that even if low-speed and high-speed expansion and contraction movements and cracks occur on the ground of the building, the formed waterproofing layer itself is easily cracked or peeled off. In order not to cause the problem, it is required to be excellent in elasticity, adhesiveness, and durability. From this point, FRP
There is a problem that the structure is inferior in crack followability due to its small elongation. This is because a stress concentration point is generated at a fixed-interval joint portion such as a rooftop waterproof structure of a building, which leads to breakage of the waterproof material.

In order to solve this problem, Japanese Patent Application Laid-Open No.
No. 42 discloses that the superior characteristics of FRP and polyurethane resin are
A structure with layers is proposed. Here, the following improvement is proposed for the interlayer adhesion between the polyurethane resin layer and the FRP layer, which is a particular problem.

That is, this is a construction method in which a plastic particulate having a particle size of 0.4 mm or more, which has good adhesiveness to the FRP resin, is added to the polyurethane resin layer side, and an integrated layer is provided. This construction structure and construction method show excellent performance with respect to the above-described concrete crack followability and the like. However, this method has the following problems.

In other words, the granular material that has appeared on the surface of the polyurethane resin layer is in contact with the FRP resin, and the adhesive strength is improved. Therefore, the granular material must uniformly appear on the surface in a convex shape. Depending on the specific gravity of the resin and the granular material, the coating method, and the change in the viscosity of the urethane resin due to the outside temperature of the coating site, the granular material may sink and not appear convex on the surface.In this case, the FRP layer and the urethane resin The adhesion of the layers is weakened.

[Means for solving the problem]

In order to solve the above-mentioned problems, the present invention provides (A) a fiber-reinforced thermosetting resin layer, (B) an adhesive layer for a fiber-reinforced thermosetting resin layer, and (C) a tensile elongation percentage specified in JISK6301 of 30% or more. Wherein the polymer composition layer provides a composite coating structure having a substrate (D) a layer of any one of a coating type resin composition layer or a synthetic polymer sheet. It is.

In this case, the polymer composition of the layer (C) may be a reinforced coating type resin composition layer mixed with a fiber reinforcing material or a synthetic polymer sheet. Further, it is preferable that (B) is a resin having an isocyanate group, and the one-component moisture-curable urethane resin layer can also serve as the (B) layer and the (C) layer.

In addition, the present invention provides an civil engineering building using the composite coated structure as a waterproof structure, applying (C) on (D), and then applying (B) having an isocyanate group, It is intended to provide a method for constructing a composite covering structure for constructing (A) thereon.

 Next, the present invention will be described in detail.

The (D) substrate used in the present invention is, for example, cement concrete, asphalt concrete, JIS5403 (asbestos slate), ALC board, PC board, FRP, plastic, wood,
It is composed of metal alone or in combination,
The shape may be any shape, and may be any of a spherical surface, a curved surface, an extended surface, a flat surface, a vertical surface, a slope, a ceiling surface, etc., as long as it is the surface of the structure.

Examples of the polymer composition layer having a tensile elongation of 30% or more as defined in (C) JIS K6301 used in the present invention include a coating type resin composition layer and a synthetic polymer sheet layer.
In the former case, a solid substrate such as concrete or metal
Base treatment, primer treatment, and the like may be performed as necessary.

The primer used between the substrate and the coating type resin composition layer is a generally known primer such as a one-part moisture-cured urethane primer, a bisphenol A type epoxy / polyamine type primer, and an unsaturated polyester type primer. .

When the material of the polymer composition layer having a tensile elongation of 30% or more is a sheet, an adhesive is used for bonding to the substrate.
This adhesive is roughly classified into an organic solvent type and a non-organic solvent type. The organic solvent system is obtained by dissolving a synthetic rubber or a synthetic resin as a main component together with an auxiliary agent in a solvent. The non-organic solvent system includes an emulsion type and a two-pack reaction type in which a main agent and a curing agent are mixed and used, and neither contains an organic solvent. This adhesive is used not only as a base and a synthetic polymer sheet, but also as an adhesive between the synthetic polymer sheets when a plurality of synthetic polymer sheets are used in a stacked manner.

Specific examples of the polymer composition layer having a tensile elongation of 30% or more in JISK6301 of (C) of the present invention are as follows. Examples of the coating type resin composition include JIS A6910 multi-layer finishing coating material, JIS-A-6021 roof waterproof coating material, and the like. JISA6
910 is a polymer cement type multi-layer finish coating material, synthetic resin Em
(Em indicates an emulsion, the same applies hereinafter) -based multi-layer finish coating material, reaction-curable synthetic resin emulsion-type multi-layer finish coating material,
A main material layer such as a synthetic resin solution type multi-layer finish coating material corresponds thereto.

The above-mentioned polymer cement type multilayer coating material of JISA6910 is a mixture of cement and a polymer dispersion for admixture as a binder. Note that the polymer dispersion is an acrylic synthetic resin or a vinyl acetate-based Em synthetic resin specified in JISA6023.

In addition, the synthetic resin Em-based multi-layer coating material is an acrylic resin, a vinyl acetate-based synthetic resin, or the like. The above-mentioned reaction-curable synthetic resin Em is a reaction-curable synthetic resin Em such as an epoxy resin. The synthetic resin solution-based multi-layer finish coating material is an acrylic resin, a vinyl-based synthetic resin dissolved in an organic solvent such as xylene or toluene, and an epoxy-based or urethane-based reaction-curable synthetic resin. It is dissolved in an organic solvent such as xylene or toluene.

JISA6021 (roof waterproofing coating material) means urethane rubber type 1 and 2, acrylic rubber type, chloroprene rubber type,
There are acrylic resin type and rubber asphalt type. Urethane rubber type 1 and 2 are two-component urethane rubber waterproofing consisting of a main ingredient mainly composed of a compound having an NCO group and a curing agent mainly composed of a crosslinking agent, a filler and the like. It is classified into Class 1 and Class 2 by its quality.

Here, the acrylic rubber based on JISA6021 is an acrylic rubber Em-based composition in which a filler and the like are blended with a non-vulcanized acrylic rubber mainly composed of an alkyl acrylate. The acrylic resin-based composition is a composition mainly composed of an acrylate ester and a methacrylate ester. The rubber asphalt type is a rubber asphalt Em composition containing asphalt and a rubber material such as styrene / butadiene or chloroprene rubber as main components. The chloroprene rubber-based is a chloroprene rubber solution-based waterproofing agent containing chloroprene as a main raw material and blending a filler and the like. The rubber asphalt-based is a rubber asphalt emulsion-based waterproofing agent containing asphalt and rubber as main components.

Preferably used in the coating type resin composition used in the present invention, considering the crack followability of the precursor, JI
Examples include products of SA6021, stretch-type synthetic resin Em-based multi-layer coating materials of JISA6910.

These various coating-type resin compositions include, in addition to the resin, aggregates, viscosity stabilizers, nonionic surfactants, antifoaming agents, antifreezing agents, dispersants, wetting agents, preservatives, pH adjusters, if necessary. ,
A part or all of a thickener, a film forming aid, various fillers, a pigment, cement, a fibrous material, and the like may be blended.

When a powder such as a filler or cement is mixed, the tensile elongation decreases. When the elongation rate is less than 30%, the crack followability becomes extremely poor. The preferred tensile elongation is
It is 50% or more, more preferably 100% or more.

The polymer composition layer composed of a synthetic polymer sheet is as follows. That is, JISA6008, JISA
A synthetic polymer roofing specified in 6009, a synthetic polymer roofing obtained by laminating a base cloth and the like.

These roofing materials include vulcanized rubber-based roofing such as ethylene propylene rubber and butyl rubber, non-vulcanized rubber-based roofing such as butyl rubber and ethylene propylene rubber, vinyl chloride-based roofing such as vinyl chloride and vinyl chloride copolymer, There are ethylene vinyl acetate copolymer resin roofing and the like. A laminate of these materials and others is a JISA6009 product.

The (B) adhesive layer for a fiber-reinforced thermosetting resin layer of the present invention is formed by applying an adhesive in a form that can be applied in a liquid state. As the type, there are urethane type, epoxy type, vinyl ester type, unsaturated polyester type, acrylic type and the like. Considering that it is on-site construction,
Urethane-based adhesives having isocyanate groups that react with moisture are preferred. The urethane-based adhesive having an isocyanate group is a moisture-curable adhesive composed of a urethane prepolymer having an isocyanate (NCO) group at a terminal obtained by reacting a polyisocyanate and a polyol.

As the isocyanate, any organic polyisocyanate used for producing a moisture-curable urethane paint can be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4 / 2,6 = 65/35
(Weight ratio) Tolylene diisocyanate, 2,4 / 2,6 = 80/20
(Weight ratio) Tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, phenylene diisocyanate, 1,5-naphthalene diisocyanate, metaxylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated 4,4 ' −
Examples include diphenylmethane diisocyanate, crude tolylene diisocyanate, polymethylene polyphenyl isocyanate, and the like. And these can be used alone or as a mixture thereof.

Further, as the polyol, any polyols conventionally used in the production of polyurethane can be used, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolethane, trimethylolpropane,
Active hydrogen-containing compounds such as castor oil, diglycerin, sorbitol, pentaerythritol and dipentaerythritol, and the above-mentioned active hydrogen-containing compounds and alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide and tetrahydrofuran alone Alternatively, an active hydrogen-containing polymer having an average molecular weight of 3,000 or less, having an average molecular weight of 2 or more, preferably an average molecular weight of 200 to 1,000 and an average functional number of 2 to 2.5, which is obtained by addition polymerization of the mixture and having two or more terminal hydroxyl groups, is used. Other polyester polyols, oil-modified polyester polyols, poly ε-caprolactone polyols, acrylic polyols, polyimines, polyamides, urea resins, melamine resins, etc., have an average molecular weight of 3,000 or less and an average number of functional groups of 1.5 or more, preferably an average molecular weight of 200 to 1,000 and an average number of functional groups of 2 ~
An active hydrogen-containing polymer of 2.5 can also be used in combination.

Both components of these isocyanates and polyols are converted into urethane prepolymers through a well-known and conventional urethane-forming reaction in such a ratio that the molecular terminals become isocyanates. Next, the urethane prepolymer is diluted with a dilutable solvent, and the resin content is 10 to 70% by weight, preferably 15 to 70% by weight.
A 50% by weight resin solution is prepared.

Typical diluting solvents are those which do not react with isocyanates such as toluene, xylene, ethyl acetate, methyl ethyl ketone or cellosolve acetate, and these are used alone or in combination to form a polyol from the beginning of the urethanization reaction. Component and organic isocyanate component.

That is, this urethanization reaction is carried out in a reaction vessel at 30 to 80 ° C. for 2 to 5 hours by adding the above-described polyol component, organic isocyanate component and solvent, and in the presence of a conventional urethanization catalyst, for 2 to 5 hours. The urethanization catalyst is, for example, a metal catalyst such as dibutyltin laurate, tin octylate or lead octylate.

The content of organic isocyanate groups in the urethane prepolymer obtained by such an operation is preferably 13 to 25%, particularly 13 to 22%, by weight of the resin solids, and the viscosity of the obtained resin solution is about 20 to 500 cps. Easy range is good.

The prepolymer having a terminal isocyanate group,
If necessary, cements, extenders, colorants, thickeners,
Various additives such as a leveling agent and an antifoaming agent are blended to form an adhesive.

After making the adhesive, painting by hand using a brush, roller brush, etc. is usually performed, but spray spray painting by a machine is also possible, and the coating film formed in this way is moist in the air Hardens.

The above is the case where the layer (B) is provided on the layer (C),
If a so-called one-pack moisture-curable urethane paint having a very small diluting solvent content, such as the one described in JP-A-57-94056, is used, the coating layer is JI
S A6021 It becomes a material compatible with the waterproofing material for roof coatings, and can maintain a large film thickness. This coating layer allows the layer (C) to function as the layer (B), and the layer (B) Even without this, the adhesion to the layer (A) can be strengthened.

As the thermosetting resin used for the (A) fiber-reinforced thermosetting resin layer in the present invention, unsaturated polyester resin,
It is a vinyl ester resin, an epoxy resin, a phenol resin or the like, and is preferably an unsaturated polymer ester resin or a vinyl ester resin.

The unsaturated polyester resin is produced by polycondensation of an α, β-unsaturated dibasic acid or an acid anhydride thereof, an aromatic saturated dibasic acid or an acid anhydride thereof, and glycols. Polyester 30 produced by using an aliphatic or alicyclic saturated dibasic acid in combination
To 80 parts by weight in 70 to 20 parts by weight of an α, β-unsaturated monomer. The vinyl ester resin is obtained by modifying the terminal of the unsaturated polyester with vinyl and the terminal of the epoxy resin skeleton with vinyl. These may be added with a thickener, a filler, a curing catalyst, a curing accelerator, a low-shrinking agent, and the like, if necessary. Particularly, the addition of a curing catalyst and a curing accelerator is useful.

Examples of the above α, β-unsaturated dibasic acids or acid anhydrides include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chlormaleic acid and esters thereof. Examples of the basic acid or its acid anhydride include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride and esters thereof. Examples of the aliphatic or alicyclic saturated dibasic acids include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof, each alone or Used in combination.

As glycols, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane, 1,3-diol, neopentyl glycol, triethylene glycol, Tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di- (4
-Hydroxypropoxydiphenyl) propane and the like, and these are used alone or in combination. In addition, oxides such as ethylene oxide and propylene oxide can also be used. Polycondensates such as polyethylene terephthalate can also be used as part of the glycols and the acid component.

Examples of the α, β-unsaturated monomer include styrene, vinyl toluene, α-methyl styrene, chlorostyrene, dichlorostyrene, vinyl naphthalene, ethyl vinyl ether, methyl vinyl ketone, methyl acrylate, ethyl acrylate, and methyl methacrylate. Acrylonitrile, vinyl compounds such as methacrylonitrile and diallyl phthalate, diallyl fumarate, diallyl succinate, unsaturated polyesters such as allyl compounds such as triallyl cyanurate and vinyl monomers or vinyl oligomers crosslinkable with vinyl ester resins. Although they are used alone or in combination, styrene is generally used.

Thickeners are chemically bonded to hydroxyl groups, carboxyl groups, ester bonds, etc. of unsaturated polyesters, etc., to form linear or partial cross-links, thereby increasing the molecular weight and increasing the viscosity of unsaturated polyester resins. Which has
For example, diisocyanates such as toluene diisocyanate, aluminum isopropoxide, metal alkoxides such as titanium tetrabutoxy, magnesium oxide,
Examples thereof include oxides of divalent metals such as calcium oxide and beryllium oxide, and hydroxides of bimetals such as calcium hydroxide. The amount of the thickener used is generally 0.2 to 5 parts by weight, preferably 100 parts by weight of the unsaturated polyester resin, preferably
It is a ratio of 0.5 to 4 parts by weight. If necessary, a small amount of a highly polar substance such as water can be used as a thickening aid. As the colorant, any of conventionally known organic and inorganic dyes and pigments can be used. Among them, those which are excellent in heat resistance, transparency, and do not significantly hinder the curing of unsaturated polyester or the like are preferably used. Can be

The fiber reinforcement used in the present invention, for example, glass fiber,
Organic fibers such as amide, aramid, vinylon, polyester, and phenol; carbon fibers; metal fibers; ceramic fibers; or a combination thereof. In consideration of workability and economy, glass fibers and organic fibers are preferable. The form of the fiber includes plain weave, satin weave, mat shape and the like, but the mat shape is preferable in view of workability, thickness maintenance and the like.
Further, it is also possible to cut a glass roving into 20 to 100 mm and use it as a chopped strand.

Fillers include calcium carbonate powder, clay, alumina powder, silica powder, talc, barium sulfate, silica powder, glass powder, glass beads, mica, aluminum hydroxide, cellulose thread, silica sand, river sand, cold water stone, marble waste,
Known materials such as crushed stones may be mentioned, and among them, glass powder, aluminum hydroxide, barium sulfate and the like are preferable because they impart translucency upon curing.

The curing catalyst acts on an unsaturated polyester resin, a vinyl ester resin, etc., for example, an azo compound such as azoisobutyronitrile, tertiary butyl perbenzoate, tertiary peroctoace, benzoyl peroxide, methyl ethyl ketone peroxide. And organic peroxides such as dicumyl peroxide, and can be used in an amount of usually 0.3 to 3 parts by weight based on 100 parts by weight of the unsaturated polyester resin.

As the curing accelerator, metal salts of organic acids, particularly cobalt salts, for example, cobalt naphthenate, cobalt actylate,
For example, cobalt acetylacetone is used.

Examples of the internal release agent include stearic acid, higher fatty acids such as zinc stearate, higher fatty acid esters, and conventionally known compounds such as alkyl phosphate esters. It can be used in a proportion of 0.5 to 5 parts by weight.

As the low shrinkage agent, a thermoplastic resin can be used, and specific examples thereof include methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate,
Lower alkyl esters of acrylic acid or methacrylic acid such as ethyl acrylate, homopolymers or copolymers of monomers such as styrene, vinyl chloride and vinyl acetate, at least one of the vinyl monomers, and lauryl methacrylate , Isovinyl methacrylate, acrylamide,
In addition to methacrylamide, hydroxyalkyl acrylate or methacrylate, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, at least one copolymer of a monomer composed of cetylstearyl methacrylate, and the like, cellulose acetate butyrate and cellulose acetate propionate Nate, polyethylene, polypropylene and the like.

In order to produce the coated structure of the present invention, a flexible polymer composition layer (C) having a tensile elongation of 30% or more is formed on a substrate (D), and the coating of the above-mentioned JISA6021 or JISA6910 is applied. In the case of a film type, the liquid composition is formed using a device such as a gold trowel or a spray. When a synthetic polymer sheet represented by JISA6008 or JISA6009 is used, it is attached to a substrate using various adhesives.

Next, after curing if (C) is a coating type, or as it is in the case of a synthetic polymer sheet, an adhesive having an NCO group, for example, is applied with a gold trowel as described above, and fiber reinforced. An adhesive layer (B) for a thermosetting resin layer is formed. By doing so, the NCO group reacts with the moisture mixed in the layer (C) or the moisture in the air attached thereto, and the adhesiveness of the adhesive layer is improved.

(B) A layer of the thermosetting resin is applied on the adhesive layer for the fiber-reinforced thermosetting resin layer, and the fiber-reinforced material is placed thereon, or the fiber-reinforced material is applied to the fiber-reinforced thermosetting resin layer. A thermosetting resin is impregnated on the adhesive layer (B) and cured to form a fiber-reinforced thermosetting resin layer (A). Also,
In order to reduce such work, a molding material (prepreg) in which the above-mentioned thermosetting resin such as SMC or BMC has been impregnated into the above-mentioned fiber reinforced material may be used.

One of the greatest objects of the present invention is to improve the crack following performance of a coating on a precursor as described above. Practically, the cracking phenomenon of the coating material often occurs when the mortar is poured on the asphalt waterproof layer by roof waterproofing or the like. Generally, this specification has a width of about 30 on the asphalt waterproof layer.
Place a holding mortar of 00 x 3000 x 60 mm in thickness, about 30
A stretch joint of mm width is provided.

In the case of repair work, a new waterproof layer will be provided directly on the holding mortar. Therefore, when the expansion joint moves due to a temperature change, a vibration of a building, or the like, stress propagates to the newly installed waterproof layer on the holding mortar, and the waterproof layer receives a load. If the load is large or the number of repetitions is large even if the load is small, the waterproof layer may be broken.

Generally, in the existing waterproof layer, as a method of solving this problem, a method called an insulation method at the joint portion, in which the body and the waterproof layer are not closely adhered, is often adopted. As a matter of course, this insulating method is also included in the construction method of the present invention, and the resulting structure is also included in the present invention.

Furthermore, as a result of various investigations to improve the follow-up performance of the joint at the joint part, when applying the flexible polymer composition layer of the layer (C), a reinforcing material having a width of about 30 to 200 mm at the upper part of the joint is arranged. ,
It is preferable that the polymer composition is applied thereon and cured to form the layer (C), or that the polymer composition is impregnated into a reinforcing material and cured to form the layer (C). Examples of the reinforcing material include the above-mentioned reinforcing materials, and a tape-like material having a width of about 100 mm, such as satin weave and plain weave, is practically preferable.

If the composite covering structure obtained in this way is used for civil engineering buildings, it can be made into a waterproof structure, and in that case, it has excellent crack following properties. It can cover and prevent water leakage.

〔Example〕

 Next, examples of the present invention will be described.

[Production of fiber-reinforced thermosetting resin layer adhesive having NCO group]

(A) "Hipox DP-2000" with molecular weight of 2000 and OH value of 56
(Bifunctional polyether polyol manufactured by Dainippon Ink and Chemicals, Inc.) 1000 g, 1,3-butylene glycol 60 g, trimethylolpropane 30 g, polymethylene polyphenylisocyanate (Crude MDI manufactured by Nippon Polyurethane Co., Ltd.)
Toluene was added to 2713 g and the resin content to 60%, and the mixture was stirred and mixed at 50 ° C to give an NCO% of 9.6 and a viscosity (25%).
C., the same applies hereinafter) to obtain a resin solution composed of a urethane prepolymer and a diluting solvent (toluene) having a viscosity of 260 cps.

Xylene as a diluting solvent was added to the resin solution obtained above to make the resin content 40%, and an adhesive (a) of a moisture-curable polyurethane resin solution having a viscosity of 27 cps was obtained.

(B) "Hipox DP-100" having a molecular weight of 1000 and an OH value of 112
0 "(a bifunctional polyether polyol manufactured by Dainippon Ink and Chemicals, Inc.) 1000 g, trimethylolpropane 90 g,
201 g of 3-butylene glycol and 2,4- / 2,6- (80/20)
Toluene isocyanate is added to 1400 g of tolylene diisocyanate so that the resin content becomes 60%, and the mixture is stirred and mixed at 60 ° C. for 5 hours. The urethane prepolymer having an NCO% of 6.5 and a viscosity of 1300 cps and a diluting solvent (toluene) are used. A polyurethane resin solution was obtained.

Xylene as a diluting solvent was added to the polyurethane resin solution obtained above to obtain a resin content of 40% and a viscosity of 17 cps.
Thus, an adhesive (b) of a moisture-curable polyurethane resin solution was obtained.

(C) PAPI (trade name) 33.6 parts by weight [Polymethylene polyphenyl isocyanate (manufactured by Kasei Upjohn Co., Ltd.)] NISSO-PB-G-1,000 (trade name) 36.4 parts by weight [polybutadiene polyol having a molecular weight of about 1,000 (Japan) Xylene (30.0 parts by weight) was reacted at 70 ° C. for 4 hours to obtain a prepolymer having the following properties.

Non-volatile content (%) 70 Viscosity (25 ° C Gardner) J Effective NCO content (%) 8.0 1 part by weight of cement was mixed with 1 part by weight of the prepolymer to prepare an adhesive (c).

Example 1 (when layer (C) is a coating film type) On a substrate (concrete or asbestos slate) as (D), Dick of polyurethane resin is used as layer (C).
A urethane waterproofing material (a mixed solution of the main agent / hardener = 50/50) was applied to a thickness of about 2 mm with a gold iron. After curing, the adhesive (a) synthesized above was applied as a layer (B) on the polyurethane resin layer at a solid content of 150 g / m ² . After the resin of the adhesive layer is cured, an unsaturated polyester resin (Polylite FR-200 manufactured by Dainippon Ink and Chemicals, Inc.) is applied as a layer (A), and a glass chop mat (450 g / m ² , Nitto) is applied thereon. (Spinning Co., Ltd.) was laid to produce a composite coated structure.
The following table shows the results of a crack following test, a fatigue test, a peeling test, and a uniaxial tensile adhesion test performed on the obtained specimen. The test method will be described later.

Examples 2 to 6 (when layer (C) is a coating film type) In the same manner as in Example 1, a specimen of a composite coated structure having a configuration described in a column corresponding to each of the following tables was prepared. Table 1 shows the results of these tests performed in the same manner as in Example 1.

Examples 7 to 10 (when layer (C) is a synthetic polymer sheet) A nitrile rubber-based adhesive DP bond E 200 g / m ² was uniformly applied on a substrate (concrete or slate) as (D). And left at 20 ° C., 60% for 30 minutes. Thereafter, the DP roof sheet as the layer (C) was sufficiently press-bonded using a rubber roll, and air was completely extruded and bonded. After that, the layers (B) and (A) in the columns of the respective examples in the following table were applied in the same manner as in Example 1, and the obtained test pieces were tested in the same manner as in Example 1. Are shown in Table 1.

Example 11 A layer (C) was laid on the substrate in the same manner as in Example 1, and an epoxy adhesive (Epiclon 5300-42 (manufactured by Dainippon Ink and Chemicals, Inc.) was used as a layer (B) thereon). / Curing agent lactamide B-3150-45 (manufactured by Dainippon Ink and Chemicals, Inc.) = 100/50) to form an adhesive layer having a solid content of 150 g / m ² . After the resin of the adhesive layer was cured, the layer (A) was provided in the same manner as in Example 1 to prepare a test body. Table 1 shows the results of the same tests as in Example 1.

Examples 12 to 13 Specimens were prepared in the same manner as in Example 11 except that the adhesive described in the column of each example in the following table was used for the layer (B), and the same test was conducted. Table 1 shows the results.

Example 14 In Example 7, an epoxy-based adhesive (Epiclon 5300-42 (Dainippon Ink Chemical Industry Co., Ltd.)
Lacqueride B-3150-45 (manufactured by Dainippon Ink and Chemicals, Inc.) = 100/50), and a test piece was prepared in the same manner as described above.
Shown in

Example 15 (when the layers (B) and (C) are used as one layer) As in Example 2, Dick Retan W (a one-component moisture-curable urethane resin solution manufactured by Dainippon Ink and Chemicals, Inc.) was used on the substrate. A test piece was formed by applying and curing to form a layer (C), and then forming a layer (A) thereon in the same manner as in Example 1.
Table 1 shows the results of the same tests as in Example 1.

Comparative Examples 1 to 5 Specimens having the configurations described in the respective comparative examples in the following table were prepared in the same manner as in the above examples, and the results of the same tests as in Example 1 are shown in Table 1.

[Test Method] Crack Following Test As shown in FIG. 1, a test piece was prepared by using a slate 1 as a substrate and providing a coating 2 of the (C), (B) and (A) layers thereon as described above. A load-elongation curve was measured using an autograph (IS-5000) (manufactured by Shimadzu Corporation). The evaluation was performed based on the load and elongation when the cover 2 provided on the substrate was broken.

Fatigue test Using the test specimens shown in Fig. 1, measurements were made in accordance with the fatigue test conditions (table) of JASS8 waterproofing construction (1986), the same as the standard specifications for construction work. The test machine used was "Hydraulic servo building finishing material fatigue tester" manufactured by Washinomiya Seisakusho.

Peeling Test Using the test specimen shown in FIG. 1, the adhesive strength of the (A) layer / (B) layer / (C) layer was measured according to JIS-S-6040.

Uniaxial Tensile Adhesion Test As shown in FIG. 2, a uniaxial tensile adhesion test was conducted by providing a coating 4 on a JIS concrete sidewalk plate (300 mm × 300 mm × 70 mm) 3 in the same manner as the coating shown in FIG. Leave for 1 week in an atmosphere at 65 ° C and a relative humidity of 65%.
A mm × 40 mm steel jig was bonded using an epoxy resin. After the adhesive was cured, it was tested at 20 ° C. at a loading speed of about 1 kgf / cm ² / sec using a hydraulic adhesion tester manufactured by Yamamoto Houkiki Co., Ltd.

 The method for calculating the tensile adhesive strength is as follows.

In the table, UPE represents an unsaturated polyester resin, and VE represents a vinyl ester resin.

Example 16 In the same manner as in Example 1, as shown in FIG.
Specimens provided with a coating 2 'composed of the layers (B) and (A) were prepared. That is, a double-sided adhesive tape is used for the gap 8 of the asbestos slate 7 'shown in FIG.
A polyethylene foam backer 9 is put in this gap portion and fixed as shown in (1), whereby the layer (C) is applied so that the applied material does not enter.
(A) The layer was formed, and the backer was removed to prepare a test piece having a coating layer. This specimen was tested in the same manner as the crack following test described above, and its elongation at break and strength were determined from the load and elongation curves. The results are shown in Table 2.

Example 17 Example 16 (C) layer and hold the glass cloth 250 g / m ² on a 2
It was inserted in a shape of 0 mm (dotted line in FIG. 3 (b)) and 50 mm in width (same as the width of the (C) layer). In the insertion method, about half of the urethane resin was applied to a predetermined size, and after curing, the glass cloth was arranged, and the other half of the urethane resin was applied from above and cured. Thereafter, layers (B) and (A) were formed in the same manner as in Example 16 to obtain a test body. Table 2 shows the results of the same tests as in Example 16.

Examples 18 to 20 In Example 17, the length of the glass cloth was 50
Specimens were prepared in the same manner, except that mm (FIG. 3 (b) dotted line, Example 18), 80 mm (FIG. 3 (b) dotted line, Example 19) and 150 mm (Example 20) were used. Table 2 shows the results of similar tests.

Example 21 In Example 21, except that the gap 8 of the slate plate 7 'was filled with a sealing material (Dick Seal # 1000, a sealing material manufactured by Dainippon Ink Co., Ltd.) instead of the backer in FIG.
(B) on the glass fiber reinforced (C) layer as in 18,
(A) A test piece having a layer in order was produced. Table 2 shows the results of the same tests as in Example 16.

Example 22 In FIG. 3, instead of the backer, the insulating tape of the void 8 of the slate 7 '(trade name: high sleeve, length 60 × width)
A test piece having (B) and (A) layers sequentially on the glass fiber reinforced (C) layer was prepared in the same manner as in Example 19 except that an insulating portion was provided. did. Table 2 shows the results of the same tests as in Example 16.

Example 23 A test piece was prepared in the same manner as in Example 18, except that the layer (C) was a coating-type plus wall of 2 mm. Table 2 shows the results of the same tests as in Example 16.

Comparative Example 6 In FIG. 3, Dick urethane was added to the slate plate 7 '.
A test piece provided with a coating film 2 mm of only JS was prepared, and the test piece was prepared in Example 16.
Table 2 shows the results of the same tests as in the above.

COMPARATIVE EXAMPLE 7 Table 2 shows the results of a test conducted in the same manner as in Example 16 by preparing a test piece having a slate plate 7 'provided with a coating film made of only FRP (using unsaturated polyester) in FIG.

[Effects of the Invention] According to the present invention, (D) the substrate has (C) a tensile elongation of 30%.
% Or more of a polymer composition layer, and a layer of a coating type resin composition layer or a synthetic polymer sheet is formed, and a (B) fiber-reinforced thermosetting resin layer adhesive layer is formed thereon. Since the (A) fiber-reinforced thermosetting resin layer is formed through the intermediary layer, the (B) layer firmly joins the (C) layer and (A), and there is no problem such as separation of the two. In particular, when the layer (B) is formed of a resin having an NCO group, the effect can be enhanced.

In addition, when a reinforcing material is used in combination with the C layer, the followability of the joint at the joint body can be improved.

In this way, an excellent composite covering structure that can withstand cracks and withstands severe fatigue tests using concrete or the like as a base is obtained. The practical value of the covering structure can be further improved. For example, regarding the salt barrier property, Class C (chloride ion permeation amount of coating film is 10 mg / cm ² ) specified in “Guidelines for salt damage prevention of road bridges (draft) and commentary” of Japan Road Association
・ Below day).

Such a composite covering structure is not only useful as a waterproof structure for a civil engineering building, but also, for example, protects concrete, and can suppress deterioration of concrete, which has become a social problem.

[Brief description of the drawings]

FIG. 1 is a perspective view of a specimen used for a crack followability test of a composite coated structure, FIG. 2 is an explanatory view of an apparatus used for a uniaxial tensile test, and FIG. 3 (a) is a joint portion of the composite coated structure. FIG. 2 is a perspective view of a test body used for a vehicle followability test, and FIG. In the figure, 2, 2 'are coatings, A is A layer, B is B layer, C is C
Asbestos slate as substrate for layers 1, 7 '.

Claims (6)

(57) [Claims] 1. From above, (A) a fiber-reinforced thermosetting resin layer, (B) an adhesive layer for a fiber-reinforced thermosetting resin layer, and (C) a polymer composition layer having a tensile elongation of 30% or more specified in JISK6301. The composite coating structure, wherein the polymer composition layer has any one of a layer of a coating type resin composition layer and a synthetic polymer sheet (D) a substrate. 2. The composite coated structure according to claim 1, wherein the coating-type resin composition layer is reinforced with a fiber auxiliary material, and the polymer composition layer (C) is a reinforcing coating-type resin composition layer. 3. The composite coated structure according to claim 1, wherein (B) contains a resin having an isocyanate group. 4. The composite coated structure according to claim 1, wherein the resin of the layer (C) is a one-component moisture-curable urethane resin layer, and the layer (C) also serves as the layer (B). 5. An civil engineering building using the composite covering structure according to claim 1 as a waterproof structure. 6. A method according to claim 1, wherein (C) is applied on (D) using the components (A) to (D).
Then, (B) having an isocyanate group is applied, and (A) is applied thereon.