JP2778070B2 - Composite covering structure, civil engineering building and construction method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial application field) The present invention relates to a crack-following property, a waterproof property, a carbon dioxide gas barrier property, a salt-shielding property, and a driving force applied to concrete and mortar structures and metal precursors. The present invention relates to a composite covering structure, a civil engineering building, and a construction method 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, a flexible unsaturated polyester resin and fiber reinforcing material are combined as in Japanese Patent Publication No. 52-25877. An FPR structure or a coated structure of a foamed polyurethane resin as disclosed in JP-A-58-189071 is known.

(Problems to be Solved by the Invention) The above-mentioned FPR structure is more excellent in water resistance, heat resistance, salt barrier property, abrasion resistance, weather resistance, gas barrier property and the like than the performance of the retained resin. 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 is associated with 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, and earthquakes, so that cracks are inevitably generated on the surface. 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 motions and cracks occur on the ground of a building, the formed waterproofing layer itself easily cracks or peels off. Stretch, so as not to cause
It is required to be excellent in adhesiveness and durability.

The FRP structure has a problem that crack followability is poor.
This is because a stress concentration point is generated at a fixed interval joint portion such as a rooftop waterproofing of a building, which leads to breakage.

On the other hand, high elongation type coating materials and structures as defined in JIS A 6021, such as polyurethane resins, have excellent tensile elongation rates compared to FRP structures, and are therefore extremely excellent in terms of sharpness followability.

However, it is inferior in other chemical and physical properties due to its resin properties.For example, salt shielding performance to protect structures from salt damage, carbon dioxide gas barrier performance to prevent carbonation of concrete, other water resistance, weather resistance There is a problem in the properties, abrasion, etc.

On the other hand, as a construction problem, there is an effect of the moisture of the concrete precursor. In particular, the carousel on the outer wall is affected by the weather and the moisture content changes significantly. The effect is particularly great during the rainy season, which is hot and heavy rain.

When the water content of the concrete increases, there occurs a problem that the interfacial adhesion between the synthetic resin coating layer and the precursor layer is reduced even if the primer is treated.

(Means for Solving the Problems) The present inventor has conducted intensive studies on these problems,
The present invention has been completed. That is, the present invention provides (A) a fiber-reinforced thermosetting resin layer, (B) an emulsion composition having a tensile elongation of 30% or more in JIS K 6301,
(C) A composite coating structure comprising a substrate, (B) a composite coating structure in which a layer contains plastic particles, and a method for applying the same.

(Configuration) The substrate (C) of the present invention is composed of, for example, cement concrete, asphalt concrete, ALC board, PC board, FRP, plastic, wood, metal, etc., alone or in combination. Any surface may be used, and any surface such as a spherical surface, a curved surface, a cylindrical surface, a flat surface, a vertical surface, a slope, a ceiling surface, etc. may be used as long as it is the surface of a civil engineering building structure. For solid substrates such as concrete and metal,
It is preferable to perform a primer treatment or the like.

Examples of the emulsion composition (B) of the present invention include a thermoplastic emulsion, a synthetic rubber-based latex emulsion, a thermosetting resin emulsion, and a post-emulsion emulsion.

Emulsions of the present invention include water-based, solvent-based, and water / solvent-based emulsions. Preferably, the constituents are composed of water and polymers, and if necessary, are composed of emulsifiers, protective colloids, and additives. It is.

When the above four types of emulsions are classified according to their production methods, they are mainly made by emulsion polymerization. In other words, the “emulsification” of the polymer formed at the same time as the “polymerization” of the unsaturated monomer
In which water-insoluble polymer is uniformly dispersed in water. In addition, there is a self-emulsification dispersion method of the polymer itself. Here, the latek is a common name when the polymer is a synthetic rubber containing butadiene or the like.

Unlike the case of the above, the polymer (synthetic resin) that has already been produced is manufactured by a method in which the polymer is finely dispersed in water to form an emulsion.

Are typically classified into the following four types. 1. Emulsion of vinyl acetate homopolymer (abbreviated as Em) 2. Em of copolymer containing vinyl acetate as a main component, ie, vinyl acetate-acrylate ester Em, vinyl acetate-dibutyl maleate Em, vinyl acetate-veova Em, vinegar to ethylene Em
etc.

3. Em of copolymer mainly composed of acrylate ester For example, acrylate ester to methyl methacrylate E
m, acrylate to styrene Em.

4. Other Thermoplastic Resins Em There are vinylidene chloride copolymer Em, vinyl chloride copolymer Em, polyurethane elastomer Em, polyethylene Em, ethylene-propylene-diene Em, silicon Em, polybutene Em and the like.

Typical examples are SBR (butadiene and styrene) and NBR (butadiene and acrylonitrile) copolymers. Other EBR latex, SB latex,
High styrene latex, MBR latex, chloroprene latex, natural rubber latex, vinyl pyridine latex, cis-1,4-polyisoprene latex, thiochol latex, butyl latex and the like.

As unsaturated polyester resin Em, epoxy resin
Em, phenolic resin Em, urethane resin Em, urea resin Em
Etc.

Examples thereof include rubber asphalt Em, asphalt Em, urethane asphalt Em, and paraffin wax Em.

On the other hand, the emulsion composition of the present invention will be described as follows according to JIS standards for easy understanding in practical use. That is, the Em-type composition layer preferable as the emulsion composition of the present invention is JIS A 6021 (coating material for roof waterproofing).
This is an Em-type material specified in JISA6910 (multi-layer finish coating material).

In other words, it is an acrylic rubber type, an acrylic resin type, or a rubber asphalt type according to JIS A 6021. In JIS A 6910, the main material layers such as a polymer cement-based multi-layer finish coating material, a synthetic resin Em-based multi-layer finish coating material, and a reaction-curable synthetic resin emulsion-based multi-layer finish coating material are equivalent.

Here, the acrylic rubber based on JIS A 6021 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 using asphalt and a rubber material such as styrene / butadiene or chloroprene as main raw materials.

The polymer cement-based multi-layer coating material of JIS A 6910 is a mixture of cement and a polymer dispersion for admixture as a binder. The polymer dispersion is an acrylic or vinyl acetate Em synthetic resin specified in JIS A 6023.

The synthetic resin Em-based multi-layer coating material is an acrylic or vinyl acetate-based synthetic resin Em.

The reaction-curable synthetic resin Em is a reaction-curable synthetic resin Em such as an epoxy resin.

The Em-type composition used in the present invention is preferably used according to JIS A60 in consideration of crack followability of the vehicle.
21 products, JIS A 6910 stretch-type synthetic resin Em-based multi-layer coating materials, etc.

These various Em compositions may be used in emulsions as needed for bone, viscosity stabilizers, nonionic surfactants, defoamers, antifreezes, dispersants, wetting agents, preservatives, pH adjusters, thickeners,
Part or all of a film forming aid, various fillers, pigments, cement, fibrous materials and the like are blended.

When a powdery substance 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.

Preferred tensile elongation is 50% or more, more preferably 100%
That is all.

The thermosetting resin of the present invention is, for example, an unsaturated polyester resin, a vinyl ester resin, an epoxy resin, a phenol resin and the like, preferably an unsaturated polyester resin,
It is 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. 30 to 80 parts by weight of an unsaturated polyester produced in combination with an aliphatic or alicyclic saturated dibasic acid as α, β
And those obtained by dissolving in 70 to 20 parts by weight of unsaturated monomers. The vinyl ester resin is obtained by modifying the terminal of an unsaturated polyester with vinyl and the terminal of an epoxy skeleton (epoxy resin) with vinyl. These may be thickeners, fillers, curing catalysts,
A curing accelerator, a low-shrinking agent and the like are added, and the addition of a curing catalyst and a curing accelerator is particularly useful.

Examples of the α, β-unsaturated dibasic acid or its anhydride include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chlormaleic acid and esters thereof, and aromatic saturated dibasic acid. Or as the acid anhydride, phthalic acid, phthalic anhydride, isophthalic acid,
There are terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride and their ester acids,
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 in combination. Used as 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-hydroxypropoxydiphenylpropane and the like can be mentioned, and they 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. α, β-unsaturated monomers include styrene, vinyltoluene, α-methylstyrene,
Vinyl compounds such as chlorostyrene, dichlorostyrene, vinyl naphthalene, ethyl vinyl ether, methyl vinyl ketone, methyl acrylate, ethyl acrylate, methyl methacrylate, acrylonitrile, methacrylonitrile, and diallyl phthalate, diallyl fumarate, diallyl succinate, triaryl Examples thereof include a vinyl monomer or a vinyl oligomer crosslinkable with an unsaturated polyester such as an allyl compound such as lucyanurate, which is used alone or in combination. In general, styrene is used.

The thickener is chemically bonded to the hydroxyl group, carboxyl group, ester bond, etc. of the unsaturated polyester to form linear or partial crosslinks, thereby increasing the molecular weight and increasing the viscosity of the unsaturated polyester resin. Which has
For example, diisocyanates such as toluene diisocyanate, aluminum isopropoxide, metal alkoxides such as titanium tetrabutoxy, magnesium oxide,
Examples include oxides of divalent metals such as calcium oxide and beryllium oxide, and hydroxides of divalent metals such as calcium hydroxide. The amount of the thickener used is usually 0.2 to 10 parts by weight, preferably 0.5 to 4 parts by weight, based on 100 parts by weight of the unsaturated polyester resin. 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, and among them, those which are excellent in heat resistance and transparency and do not significantly hinder the curing of the unsaturated polyester resin are preferable.

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.

Further, the form of the fiber includes plain weave, satin weave, mat shape and the like, but the mat shape is preferable from the viewpoint of workability and thickness maintenance.
It is also possible to cut the 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.

As the curing catalyst, those acting on the unsaturated polyester resin, for example, an azo compound such as azoisobutyronitrile, tertiary butyl perbenzoate, tertiary peroctoate, benzoyl peroxide,
Organic peroxides such as methyl ethyl ketone peroxide and dicumyl peroxide can be exemplified, and they can be used usually in a range of 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 octylate,
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. 0.5
It can be used in a proportion of up to 5 parts by weight.

The low-shrinking agent is a thermoplastic resin, and specific examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, lower alkyl esters of acrylic acid or methacrylic acid such as ethyl acrylate, styrene, vinyl chloride, and acetic acid. Homopolymers or copolymers of monomers such as vinyl, at least one of the vinyl monomers, lauryl methacrylate, isovinyl methacrylate, acrylamide, methacrylamide, hydroxylalkyl acrylate, or methacrylate, acrylonitrile, methacryloyl Nitrile,
In addition to copolymers of at least one kind of monomer composed of acrylic acid, methacrylic acid, and cetylstearyl methacrylate, there are cellulose acetate butyrate, cellulose acetate propionate, polyethylene, polypropylene and the like.

The plastic granules contained in the emulsion composition of the present invention have a particle size of 0.4 mm or more. If the particle size is smaller than this, the interlayer adhesion strength between FRP and the emulsion type composition cannot be improved only by increasing the viscosity. Usually the particle size is 0.4 to 10 mm, preferably 1 to 10 mm, especially 1 to 6 mm
In, the specific gravity is 0.02 to 1.4, particularly preferably 0.03 to 1.0,
For example, styrene-butadiene copolymer, saturated polyester, acrylic resin, polybutadiene, polyurethane elastomer, polystyrene, ABS, PVC, EVR, SBR, nylon, petroleum resin, butyl cellulose acetate, styrene butadiene polymer, plastics such as polyamide Granules can be used. Particularly preferably, when the FRP layer is applied in situ at room temperature, the styrene is used for the structure of the FRP layer since the adhesive strength between the emulsion type composition layer and the FRP layer is strengthened by dissolving the particulate matter in the reactive monomer. It is a styrenic polymer granule held in it. Styrene in the polymer may be used alone or in the form of a two-component, three-component or other multi-component copolymer. Examples of the former include a polystyrene resin containing a rubber component such as butadiene and a styrene acrylonitrile copolymer.

ABS is a three-component form. Further, a granular material of a styrene derivative may be used, and examples thereof include methylstyrene, α-methylstyrene, and dichlorostyrene. Further, it may not contain styrene or may be a granular material having good compatibility with the reactive monomer such as acryl. The particulate matter may be mixed in advance with the emulsion type composition, may be used by mixing immediately before the application, or may be sprayed immediately after the application of the emulsion type composition. The amount of the particulate matter to be added is preferably 1 to 700 parts by weight, especially 1 to 300 parts by weight based on 100 parts by weight of the solid content of the emulsion. 1-5 for waterproof layer
It is about 0 parts by weight.

The effect on the physical properties of the presence or absence of the plastic granules is remarkably exhibited in crack followability. That is, the granular material is (B)
The FRP (A) layer breaks in the structure because the (A) layer and the (B) layer have good adhesiveness when they are contained in the layers. At this time, the emulsion composition (B) layer was not broken.

Conversely, when no particulate matter is added, the FRP (A) layer and (B)
Since the adhesiveness of the layers is poor, the layers (A) and (B) peel off in a state where the FRP (A) layer is not broken.

However, if the layer (B) to which no particulate matter is added does not adhere to the FRP (A) layer at all, the load does not increase, but
The reason why there is a breaking load of about 0 to 120 kg is considered to be due to adhesion to some extent. The adhesion between the layer (A) and the layer (B) is due to the fact that the emulsion (B) layer is dissolved in styrene as a reactive monomer, the relationship between polar groups, and fine irregularities on the surface due to the filler in the emulsion composition. Of the adhesive effect due to the anchor effect.

Further, the effect of the FRP layer (A) is to impart performance excellent in gas permeability and salt barrier properties. Therefore, although the deterioration of concrete has become a very social problem in recent years, the present invention is also very excellent as a protective covering material for concrete. Regarding the salt barrier property of the present invention, Class C (chlorine ion permeation amount of the coating film is 10 ^-3 ) specified in “Guidelines for Measures against Salt Damage on Road Bridges (Draft) and Explanation” of the Japan Road Association.
mg / cm ² day). Furthermore, since the adhesiveness between the substrate and the emulsion type composition (B) and the adhesiveness between the emulsion type composition and (B) and FRP are excellent, an excellent waterproof layer can be obtained by taking advantage of the excellent water resistance of FRP.

As other effects of the structure of the present invention, when the emulsion type composition layer (B) is used as a floor structure, effects such as a heat insulating effect, a cushioning property, and a sound insulating property are obtained.

As described above, the structure of the present invention can be used as a protection structure such as a waterproof layer for civil engineering and buildings, and further as a structure such as a floor, a ceiling, and a wall. Furthermore, as a heat insulating structure, a wall,
It can be used for tanks, bathrooms, pipes and the like.

Hereinafter, the present invention will be described with reference to examples. “Parts” in the examples indicates parts by weight. These examples illustrate one embodiment of the present invention and do not limit the present invention.

The evaluation tests were categorized as follows: (1) layer (B), substrate (C)
(2) Various physical tests of the composite structure were performed.

In the test (1), the surface moisture was changed according to the wetting conditions of the substrate, one of which was the curing time of the concrete. The creation conditions and others are as follows.

The concrete having the composition shown in Table 1 was kneaded with a tilted concrete mixer (Model MIC-109-0-02) manufactured by Marui Co., Ltd., and cast into a stainless steel mold having a thickness of 3 mm and an open surface. The weight of one test specimen was about 6 kg.

After the casting, intensive curing was carried out in a constant temperature room of 20 ° C / 65% with the open side facing upward. For the water content on the concrete surface, a CH-2 type high-frequency moisture content system of Kett Co., Ltd. was used. Incidentally, the water content of the commercially available JIS sidewalk version was 8 to 9%.

After completion of the prescribed curing time, the layer (B) was constructed with a thickness of 2 to 5 mm.

(B) After coating the layer, it was allowed to stand for about one week, and a uniaxial tensile adhesion test was performed by the method as shown in FIG. In the tensile test, a 40 × 40 mm steel adhesive plate was bonded to the cut in the ascon portion using an epoxy adhesive. After the adhesive was cured, a test was performed at 20 ° C. at a loading speed of about 16 kgf / cm ² / sec using a hydraulic adhesion tester manufactured by Yamamoto Houkiki Co., Ltd.

The calculation method is Another method to see the effect of the wet state on the adhesion is to leave a JIS concrete sidewalk plate (300 x 300 x 70 mm) in a semi-water state for three months as shown in Fig. Apply the emulsion type composition (B) to the surface,
A tensile adhesion test was performed in the same manner as described above.

As the evaluation test of the composite structure of (2), the following three types of tests were performed.

Three types of free film specimens: a basic physical property test, an oxygen permeability test (ASTM D-3985), and a salt barrier test were performed. In the oxygen permeability test, if oxygen is measured, the permeation amount of carbon dioxide is also measured as a calculated value. As a method for preparing a free film specimen, a silicone release agent was applied on a glass plate to prepare a specimen of about 300 × 300 × thickness, and the specimen was cut in accordance with each test.

A crack following test was carried out on this test piece, in which a slate plate was used as a substrate and the emulsion type composition (B) layer and the FRP layer (A) were lined thereon.

A concrete plate is used as a substrate, and an emulsion composition (B) layer and an FRP layer (A) are lined thereon as described above. The composition of the concrete is the same in Table 1, but the shape is different in each test. A blister generation test and an integrity test were performed.

<Test Method> (a) Oxygen permeability test (test specimen) The test was carried out in accordance with ASTM D-3985.

(B) Salt barrier test (test body) A coating film is sandwiched between acrylic cells, and 3% saline is put into the cells on the surface side of the coating film and distilled water is put into the cells on the surface side. After leaving at 20 ° C. for 30 days, a certain amount of the solution is collected from the cell on the distilled water side, and the chlorine ion in the solution is measured. The analysis of chloride ions was performed using an automatic potentiometer, and the amount of permeated chloride ions was determined by the following equation.

V: Distilled water volume on the back side of coating film (ml) C: Chloride ion concentration (ppm) A: Permeation area (cm ² ) Quality test method for concrete coating materials according to the Japan Road Association's “Guidelines for Salt Damage on Road Bridges / Comments” by.

(C) Crack followability test (specimen) This test was conducted based on the "Architectural crack resistance" test method of JASS 8 waterproofing coating film waterproofing material of the Architectural Institute of Japan. However, slate plate 9mm
The evaluation method was shown by the gap distance of the slate plate when the covering structure was broken.

(D) Integrity test (test piece) The test was performed under the following conditions in accordance with the method of JIS A 6910.

Conditions for leaving test specimens a. Leaving in air 7 days in an atmosphere of 20 + 1 ° C and 65 + 5% RH.

B. Leave in semi-water Leave under the conditions according to JIS A 6910. 20 + 1 ° C, 65+
7 days in an atmosphere of 5% RH.

C. Leave in water Leave in water at a water temperature of 20 + 1 ° C for 7 days.

The test results are shown in Tables 2 to 4 together with each component.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a tensile adhesion test method, and FIG. 2 illustrates a method of leaving a substrate in semi-water for performing an adhesion test in a wet state.

Claims (5)

(57) [Claims] 1. A composite coating comprising: (A) a fiber-reinforced thermosetting resin layer, (B) an emulsion-type composition layer having a tensile elongation of 30% or more according to JISK6301, and (C) a substrate from the top. Structure. 2. The structure according to claim 1, wherein the layer (B) comprises an emulsion-type composition having a tensile elongation of 30% or more and containing plastic particles having a diameter of 0.4 mm or more. 3. A civil engineering building using the structure according to claim 1 as a waterproof layer. 4. An emulsifying composition layer (B) having a tensile elongation of 30% or more according to JISK6301 on a substrate (C), and then a fiber-reinforced thermosetting resin layer (A) is provided. Characteristic structure construction method. 5. A plastic granule having a diameter of 0.4 mm or more is applied on a substrate (C) so as to be visible on the surface of an emulsion type composition layer (B) having a tensile elongation of 30% or more according to JISK6301; Next, a fiber reinforced thermosetting resin layer (A) is provided.