JPH01219242A - Combined covering structural body and execution of work - Google Patents

Abstract

PURPOSE:To improve bonding strength and follow-up performance to a base body, by setting a polyurethane resin layer including the grain plastics of the diameter of 0.4mm or larger, on the base body, and by setting a fiber reinforced thermosetting resin layer 13 on the polyurethane resin layer. CONSTITUTION:On a base body 9 a polyurethane resin layer 11 is set via a primer 10, and on the layer 11, a fiber reinforced thermosetting resin layer 13 is set. The polyurethane resin layer 11 includes the grain plastics 2 of the diameter of 0.4mm or larger. As a result, the layer bonding strength of the polyurethane resin layer 11 and the fiber reinforced thermosetting resin layer 13 is improved, and the performance of followed-up to the crack of the base body 9 is improved.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention is applicable to concrete and mortar structures, metal frameworks, with crack followability, waterproofness, carbon dioxide gas barrier properties, salt barrier properties, and structural properties. Due to its integral nature, it has excellent pre-star resistance and is related to the following composite covering structure and construction method.

(Prior art) As a waterproof coating film type structure based on a concrete structure or a metal frame, as shown in Japanese Patent Publication No. 52-25877, a flexible unsaturated polyester resin and a fiber reinforcing material are combined. FRP structure or % 1989-189
A coating structure made of a polyurethane foam resin, such as No. 071, is known.

(Problems to be Solved by the Invention) The FRP structure described above has better water resistance, heat resistance, salt resistance, scratch resistance, weather resistance, sparring resistance, etc. than the resin properties it holds. However, since the fiber reinforcing material is mixed, there is a drawback that the elongation of the material is extremely small. This drawback is associated with the following problems.

That is, in buildings made of concrete or mortar, cracks inevitably occur on their surfaces because drying shrinkage, ground subsidence, earthquakes, etc., and low-speed and high-speed expansion and contraction occur repeatedly. Since such cracks cause water leakage, it is necessary to perform waterproofing construction on these buildings.

In general, when carrying out such waterproofing construction, the waterproofing material that is applied must be able to easily maintain the formed waterproof layer itself even if slow or high speed expansion and contraction movements or cracks occur on the building surface. Stretchable, so as not to crack or peel.
It is required to have excellent adhesiveness and durability.

FRP structures have a problem of poor crack followability.

This is because stress concentration points occur in areas where joints are cut at regular intervals, such as in roof waterproofing of buildings, which can lead to breakage.

On the other hand, the tensile elongation height of the polyurethane resin structure is FR
Since it is superior to the P structure, it is extremely excellent in terms of sharpness followability.

However, on the other hand, the resin properties are inferior to other chemical and physical properties, such as salt barrier performance to protect structures from salt damage, and carbon dioxide gas barrier performance to prevent carbonation of concrete. There are problems with water resistance, weather resistance, scratch resistance, etc.

(Means for Solving the Problems) In this situation, the present inventors took advantage of the excellent fc characteristics of FRP and 4-urethane resin. After conducting intensive research on a structure in which an FRP layer is provided on a polyurethane resin layer, the inventors discovered a problem in that the interlayer adhesive strength between the polyurethane resin layer and the FRP layer was weak.As a result of further intensive research, the present invention was completed. .

That is, the present invention includes (2) a fiber-reinforced thermosetting resin layer from above;
(c) A composite covering structure consisting of a polyurethane resin layer containing plastic granules with a particle size of 0.4 mm or more, (C) a substrate, and on the substrate (C), a polyurethane resin layer containing plastic granules with a particle size of 0.4 mm or more. The present invention provides a construction method characterized by applying the layer so that it is visible on the surface of the layer () and then providing a fiber-reinforced thermosetting resin layer (A), which is particularly useful as a waterproof layer for civil engineering buildings. .

(Structure) The substrate of the present invention includes, for example, cement concrete, asphalt concrete, ALC board, PC board, FRP,
It is made of plastic, wood, metal, etc., singly or in combination, and can be of any shape, such as spherical, curved, cylindrical, flat, vertical, sloped, ceiling, etc. Either is fine. ; For solid substrates such as concrete and metal, it is recommended to perform surface treatment, primer treatment, etc. as necessary.

The primer used in the present invention is a generally known primer, such as a liquid temperature air curing type urethane glitter, a bisphenol A type epoxy/polyamine type f-) primer, or an unsaturated polyester type primer.

The polyurethane resin layer (B) of the present invention is a non-foamed or foamed polyurethane resin. The polyurethane resin contains, for example, active hydrogen-containing compounds such as polyether polyol, polylactone polyol, polycarbonate polyol, polytetramethylene glycol, polybutadiene polyol or polyester polyol, organic polyisocyanates, catalysts, chain extenders, blowing agents, if necessary, etc. Foam stabilizers, additives, etc. are used and can be obtained by appropriately setting the type of catalyst, the amount of catalyst used, the concentration of incyanate groups, the number of functional groups, etc. to match the temperature of the environment. In particular, the trap is preferably made of foam to provide insulation and cushioning properties. For example, a mixed catalyst of an amine catalyst or a metal catalyst, preferably a tin compound,
It is obtained by adjusting the incyanate group content to 1 to 50% by weight, preferably 2 to 20% by weight, and the number of functional groups to 2 to 6/molecule, preferably 2 to 3/molecule.

As the one-ether 4-liol mentioned here, any polyether 4-liol conventionally used in the production of polyurethane foam can be used, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and 1,3-butanediol. ,1,4
mm butanediol, 1,6-hexanediol, neopentyl glycol, viscoenol A%) IJ methylol ethane, trimethylol deronone, chrycerin,
These monomers and amine monomers such as ethylene diamine, urea, monomethyl jetanolamine, and monoethyl jetanolamine are further combined with alkylene oxides such as ethylene oxide, sorbitol, etc. , propylene oxide, butylene oxide, styrene oxide, etc. alone, a copolymer, or a mixture of these polymers can be used. Its number average molecular weight is preferably 500 to 100
It is 00. Further, as the polyester polyol, a condensate of a polybasic acid and a polyhydric alcohol is used, and for example, a condensate of a polybasic acid and a polyhydric alcohol is used. , diderogylene gellicol, 1,3-butanediol, 1,4 mm butanediol, 1,6-hexanediol and the like, which can be used alone or in combination with polyester polyols having terminal OH groups. Its number average molecular weight is preferably 500 to 10,000. Preferably, polyether polyols are used, which are liquid at room temperature and easy to handle.

As the chain extender, the above-mentioned polyol monomer, polyhydric alcohol, or all of the above-mentioned alkylene oxides may be used.
~2 mole added polyol and a low molecular weight polyester-diol, the number average molecular weight of which is less than 500.

As the organic polyisocyanate, any organic polyisocyanate used in the production of polyurethane foam can be used, such as 2.4 mm ) lylene diisocyanate, 2.6-) lylene diisocyanate, 2.4
/ 2.6 = 65/35 (wt)) lylene diisocyanate, 2.4 / 2.6 = 80/2
0 (wt)), 414'
-diphenylmethane diisocyanate, hexamethylene diisocyanate, phenylene diisocyanate), 1.
5-S7 Tale diisocyanate, metaxylylene diisocyanate, hydrogenated tolylene diisocyanate, water m
Examples thereof include 4.4'-diphenylmethane diisocyanate, crude tolylene diisocyanate, and polymethylene I liphenyl isocyanate. These can be used alone or as a mixture. Furthermore, prepolymers containing terminal incyanate groups obtained by reacting the polyether polyols or polyester polyols with organic I reinocyanates may be used alone or in mixtures thereof.

The blowing agent used to form the foam includes water or low-boiling organic solvents conventionally used in the production of polyurethane foam, such as trichloromonofluoromethane, dichlorofluoromethane, monochlorodifluoromethane,
Trichlorotrifluoroethane, dichlorotetrafluoroethane, methylene chloride, 1,2-dichloroethane, 1.1,2.2-tetrachloroethane, 1,1.1
-) Dichloroethane, acetone, ethyl ether, petroleum ether, etc. can be used alone or in mixtures, and preferably water is useful because it is easy to handle.

As a catalyst for adjusting the foam curing speed when forming a foam, known tertiary amine catalysts such as triethylamine, triethylenediamine, N-methylmorpholine, N
-Ethylmorpholine, N,N'-dimethylalkylamine, N,N'-diethylalkylamine, N,N,N'
, N'-tetramethylpropylene diamine, hexamethylenetetramine, etc. can be used alone or in mixtures, and metal compound catalysts such as naphthenic acid; parto, tin naphthenate, zinc naphthenate, lead naphthenate, zinc octylate. , tin octylate, lead octylate, dibutyltin dilaurate, dimethyltin dilaurate, tri-n-butyltin acetate, tin chloride and the like can be used alone or in mixtures. Particularly preferably, a mixed catalyst of tertiary amines and a tin compound is used. When forming a non-foamed material, only the metal catalyst described above is used.

In addition, as a foam stabilizer when forming a foam, known surfactants such as polymethylsiloxane, diethylaminooleate, sodium dioctyl sulfonate, nrubitan monostearate, glycerin monooleate, etc. may be used alone or in mixtures. I can do it.

In the present invention, when the substrate is a spherical surface, curved surface, vertical surface, slope, or ceiling surface, in order to increase the viscosity and prevent sagging,
It is preferable to add a powdered additive on the order of microns to the polyurethane resin. Examples of additives include whiskers, aluminum powder, copper powder, silica stone, diatomaceous earth, alumina, calcium carbonate, gypsum, mica, clay, talc, asbestos, graphite, carden fiber, glass fiber, glass powder, cement, Examples include linter, linen, wood flour, synthetic resin powder, tire powder, pigments, etc. alone or in mixtures.

Examples of plasticizers include dibutyl phthalate, dioctyl heptatalate, dibutyl maleate, dibutyl fumarate, cyoctyl adihate, ethylene glycol dibenzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, chlorinated Paraffin, petroleum resin, xylene resin, petroleum-based high boiling point solvents, etc. can be used alone or in mixtures.

The glass granules contained in the polyurethane resin in the present invention have a particle size of 0.4 mm or more.

If the particle size is smaller than this, just increase the viscosity and it will become FRP.
It is not possible to improve the interlayer adhesive strength between the polyurethane resin and the polyurethane resin.

Usually the particle size is 0.4 to 10 m, preferably 1 to 10 m,
In particular, the specific gravity is 1 to 6, and the specific gravity is 0.02 to 1.4, particularly preferably 0.03 to 1.0, such as styrene butadiene polymer, saturated polyester, acrylic resin, I liptadiene, polyurethane distomer. , I listyrene, A
BS, PVC.

Particulate plastics such as EVR, SBR, nylon, petroleum resin, butyl cellulose acetate, styrene butadiene polymer, and polyamide can be used.

Particularly preferably, when the FRP layer is installed on-site at room temperature, styrene is contained in the structure because the particulate matter is dissolved in the solvent to further strengthen the adhesive strength between the polyurethane resin layer and the FRP layer. It is a styrenic polymer granule. The styrene in the I-ref can be used alone or in the form of a multi-component copolymer such as a two-component or three-component copolymer. Examples of the former include polystyrene resins containing rubber components such as butadiene, and styrene-acrylonitrile copolymers.

A three-component type is ABS. Further, granules of styrene derivatives may be used, such as methylstyrene, α-methylstyrene, dichlorostyrene, and the like.

The granules may be mixed with the urethane resin in advance, or may be mixed and used immediately before construction, or the granules may be sprayed immediately after the polyurethane resin is applied.

The amount of the granules added is preferably 1 to 700 parts by weight, particularly 1 to 300 parts by weight, per 100 parts by weight of the polyurethane resin.
Parts by weight. The amount of the waterproof layer is about 1 to 50 parts by weight.

The thermosetting resin of the present invention includes, for example, unsaturated polyester resin, vinyl ester resin, epoxy resin, phenol resin, etc., and preferably unsaturated polyester resin,
It is a vinyl ester resin.

The unsaturated polyester resin is produced by polycondensation of α,β-unsaturated dibasic acid or its acid anhydride, aromatic saturated dibasic acid or its acid anhydride, and glycols, and in some cases, an acid component 30 to 80 parts by weight of an unsaturated polyester produced in combination with an aliphatic or alicyclic saturated dibasic acid, gold, and 70 to 20 parts by weight of α,β-unsaturated monomers.
Parts by weight (includes those obtained by dissolving. Vinyl ester resins are unsaturated polyesters with vinyl-modified ends, and epoxy skeletons (epoxy resins) with vinyl-modified ends. If necessary, thickeners, fillers, curing catalysts, curing accelerators, low shrinkage agents, etc. are added, and the addition of curing catalysts and curing accelerators is particularly useful.

As α,β-unsaturated dibasic acid or its acid anhydride;
maleic acid, maleic anhydride, fumaric acid, itaconic acid,
Examples include citraconic acid, chlormaleic acid, and esters thereof, and examples of aromatic saturated dibasic acids or their acid anhydrides include phthalic acid, 7-thalic anhydride, isophthalic acid, terephthalic acid, nitroathalic acid, tetrahydrophthalic anhydride, Endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride, and their esters are aliphatic, aliphatic or alicyclic saturated dibasic acids such as citric acid, malonic acid, uccinic acid, adipic acid, and cepacic acid. , azelaic acid, glutaric acid, hexahydroheptalic anhydride, and esters thereof, each of which may be used alone or in combination. Glycols include ethylene glycol, propylene glycol, diethylene glycol,
Diethylene glycol, 1,3-butanediol, 1.
4mm butanediol, 2-methylpropane, 1.3-
Diol, neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5-bentanediol, 1.6-hexanediol, bisphenol A1 hydrogenated bisphenol A1 ethylene glycol carbonate, 2.2-di+4mm hydroxyl glycol? Examples include xydiphenyl + propane, which can be used alone or in combination, but oxides such as ethylene oxide and zolobile/oxide can also be used. Further, polycondensed metals such as polyethylene terephthalate can also be used as part of the glycols and acid components. α, β-unsaturated monomers, styrene, vinyltoluene, α-methylstyrene, chlorstyrene, dichlorostyrene, vinylnaphthalene, ethyl vinyl ether, methyl vinyl ketone, methyl acrylate, ethyl acrylate, methyl meth Examples include vinyl monomers or vinyl oligomers that can be crosslinked with unsaturated polyesters such as vinyl compounds such as acrylate, acrylonitrile, and methacrylonitrile, and allyl compounds such as diallyl phthalate, diallyl 7-malate, diallyl succinate, and triallyl cyanurate. It can be used alone or in combination, but styrene is generally used.

Thickeners chemically combine the hydroxyl groups and cals possessed by unsaturated polyesters with xyl groups and ester bonds to form linear or partially cross-linked bonds, increasing the molecular weight and increasing the viscosity of unsaturated polyester resins. Those having metallic properties such as diincyanates such as toluene diisocyanate, metal alkoxides such as aluminum isopropoxide and titanium tetrabutoxy, oxides of divalent metals such as magnesium oxide, calcium oxide and beryllium oxide, and calcium hydroxide. Examples include hydroxides of divalent metals such as. The amount of the thickener used is usually 0.2 to 10 parts by weight, preferably 0.5 to 4 parts by weight, per 100 parts by weight of the unsaturated polyester resin. And if necessary, a small amount of a highly polar substance such as water can be used as a thickening agent.

As the colorant, conventionally known organic and inorganic dyes and pigments can be used, but among them, those that have excellent heat resistance and transparency and do not significantly interfere with the curing of the unsaturated/17 ester resin are preferred. .

The fiber reinforcing material used in the present invention is, for example, glass fiber, organic fiber such as amide, aramid, vinylon, polyester, phenol, carbon fiber, metal fiber, ceramic fiber, or a combination thereof. When considering workability and economic efficiency, glass fibers and organic fibers are preferable.Fiber forms include plain weave, satin weave, matte, etc., but matte is preferable in terms of workability and thickness retention. . It is also possible to cut the glass roving into pieces of 20 to 100 mm and use it as chopped strands.

As fillers, calcium carbonate powder, clay, alumina powder, silica powder, Merck, barium sulfate, silica powder, glass powder, f-lass beads, mica, aluminum hydroxide, cellulose thread, crushed sand, river sand, kansui stone, astronomical stone Known materials such as scraps and crushed stones can be used, and among them, glass powder, aluminum hydroxide, barium sulfate, etc. are preferable because they provide transparency after curing.

The curing catalyst is one that acts on unsaturated I-lyester resins, such as azo compounds such as azoisobutyronitrile, tert-butyl perbenzoate, tert-peroctoate, penzoyl-oxide,
Examples include organic peroxides such as methyl ethyl ketone I, monooxide, and dicumyl peroxide, and are usually 0.3 to 100 parts by weight per 100 parts by weight of unsaturated polyester resin.
It can be used in a range of 3 parts by weight.

As hardening accelerators, metal salts of organic acids, especially cobalt salts, such as cobalt naphthenate, cobalt octylate, cobalt acetylacetone, etc., are used.

Examples of the internal mold release agent include conventionally known ones such as higher fatty acids such as stearic acid and zinc stearate, higher fatty acid esters, and alkyl phosphate esters.
Usually 0.0% per 100 parts by weight of unsaturated polyester resin.
It can be used in a proportion of 5 to 5 parts by weight.

The low shrinkage agent is a thermoplastic resin, and specific examples include lower alkyl esters of acrylic acid or methacrylic acid such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, and ethyl acrylate, styrene, vinyl chloride, and acetic acid. Homopolymers or copolymers of monomers such as vinyl, at least one of the vinyl monomers and lauryl methacrylate, invinyl methacrylate, acrylamide, methacrylamide, hydroxyalkyl acrylate or methacrylate, acrylonitrile, methacrylaterile, Examples include copolymers of at least one monomer consisting of acrylic acid, methacrylic acid, and cetylstearyl methacrylate, as well as cellulose acetate butyrate, cellulose acetate propionate, polyethylene, polypropylene, and the like.

In the structure of the present invention, a primer is coated on the base (c) as necessary to form the entire primer layer, and then a polyurethane resin containing plastic particles is applied with a metal trowel or the like, or a polyurethane resin is coated on the base (c). After coating, before the resin hardens, plastic granules are sprinkled on the surface of the polyurethane resin so that the granules are visible on the surface of the polyurethane resin to form a polyurethane resin layer (B)'. Then, either a thermosetting resin is applied on the resin layer (B) and a fiber reinforcing material is placed thereon, or a fiber reinforcing material is placed on the resin layer (B) and impregnated with the thermosetting resin. FRP layer (A)? Form. In addition, in order to reduce this work, SMSMC5B
A molding material (prepreg) in which the fiber reinforcing material is already impregnated with resin may also be used. Further, when an FRP molded product is used on the resin layer (B), a structure is formed by heating the FRP molding and applying pressure if necessary to melt and bond the granules.

(Effects) The composite covering structure of the present invention obtained in this manner is made of a combination of a polyurethane resin layer (B) containing plastic particles with a particle size of 0.4 f1 or more and an FRP layer (A). Since the effect of improving interlayer adhesion strength can be obtained, excellent performance can be obtained in crack tracking performance of substrates such as concrete, and FRP
The layer (A) has excellent gas permeability and salt blocking properties. Therefore, although the deterioration of concrete has become a serious social problem in recent years, the present invention is also very excellent as a protective coating material for concrete. Regarding the salt shielding property of the present invention, it is specified in the Japan Road Association's "Guidelines for Salt Damage Countermeasures for Road Bridges (Draft) and Commentary". ~・day or less)
It passes the test. Furthermore, since the adhesion between the substrate and the polyurethane resin and the adhesion between the polyurethane resin and FRP are excellent, an excellent waterproof layer can be obtained by taking advantage of the good water resistance of F'RP. It also excels in the pristaring test, which evaluates heat and humidity properties.

Other effects of the structure of the present invention include, when the foamed polyurethane resin layer is used as a floor structure, it has a heat insulation effect,
Furthermore, effects such as cushioning properties and sound insulation properties can be obtained.

As described above, the structure of the present invention can be used as a protective structure such as a waterproof layer for civil engineering and building structures, and also as a structure for floors, ceilings, walls, etc. Furthermore, it can be used as a heat insulating structure for walls, tanks, bathrooms, pipes, etc.

The present invention will be explained below with reference to Examples. "Parts" in Examples indicate parts by weight. These examples illustrate one embodiment of the present invention, and the present invention is not limited thereto.

The test specimens for the evaluation tests were classified into three types.

(2) Free film test specimen: Three types of tests were conducted: basic physical property test, oxygen permeability test (ASTM D-3985), and ring linkage test. In the oxygen permeability test, if oxygen is measured, the permeation amount of carbon dioxide is also measured as a calculated value. The free film test specimen was prepared by applying a silicone mold release agent onto a glass plate to prepare a test specimen with a thickness of approximately 300×300×, and the specimen was cut according to each test.

(2) A crack followability test was carried out on this specimen, using a slate board as a base, applying a primer thereon, and applying two coats of a polyurethane resin layer and an FRP layer.

■ Use a concrete board as a base, apply a primer on it, and line it with a polyurethane resin layer and an FRP layer in the same way as in ■. The mix of concrete is the same as shown in Table 1, but the shape is different in each test. A blister generation test and a integrity test were conducted.

<Test method> (a) Oxygen permeability test (test specimen ■) It was conducted in accordance with ASTM D-3985.

←) Linkage test (test specimen ■) A coating film is sandwiched between acrylic cells, and 3 liters of salt solution is poured into the cell on the surface side of the coating film, and distilled water is poured into the cell on the surface side. After being left at 20°C for 30 days, a certain amount of the cell solution on the distilled water side is collected and the chloride ions in the solution are measured.

Chlorine ion analysis was performed using an automatic potential difference adjustment device, and the amount of chlorine ion permeation was calculated using the following formula.

V: Volume of distilled water on the back side of the paint film (b) C: Chlorine ion concentration (ppm) A: Permeation area (according to the concrete coating material quality test method of the Japan Road Association "Guidelines and Commentary on Salt Damage Countermeasures for Highway Bridges") .

(c) Crack followability test (test specimen ■) Architectural Institute of Japan J
ASS 8 Waterproofing work The test was carried out based on the 1. Base crack resistance test method for coating film waterproofing materials. However, slate board 9 dragon was used.
The evaluation method was expressed as the gap distance in the slate plate when the covering structure breaks.

B) Integrity test (test specimen ■) It was conducted under the following conditions in accordance with the method of JIS A 6910.

Test specimen storage conditions I, leave it in the air 7 days in an atmosphere of 20+1℃ and 65+5SRH.

Leave in semi-submerged water under conditions compliant with JIS A 6910. 20
+1” C165 + 5% RH atmosphere for 7 days.

Ha, left in water Discharged for 7 days in water at a water temperature of 20+1’C.

(e) Blister generation test (test specimen ①) Using the testing machine shown in FIG. 1, the test specimen was set as shown in FIG. A water/sand mixture was placed below the specimen to generate steam. The test device was placed in a hot air dryer at 60° C. for 3 hours, and the state of swelling on the surface was visually observed.

[Evaluation method]

○... No change It was prepared using an Eirich type concrete mixer (MIC-108-1 type manufactured by Marui Co., Ltd.) using a mixture as shown in 1. For the mold frames, we created wooden frames of each size and poured mixed concrete into them. Curing conditions are underwater curing 1
Air curing (20° C./65%) was performed for 2 weeks.

After curing, a coating layer was applied.

(Preparation of 7" repolymer A) 500 parts of I-lyoxypropylene glycol (hereinafter abbreviated as PPG) with an average molecular weight of 2000, polyoxypropylene triol (hereinafter abbreviated as PPT) with an average molecular weight of 3000.
590 parts, 45 parts of 1.3-2 tandiol, 398 parts of tolylene diisocyanate (2,4/2.6-80/20 (weight ratio) hereinafter referred to as T-807DI), dioctyl phthalate (hereinafter referred to as DOP) 360 parts of Df repolymer A with a terminal incyanate group content of 5.9 To (Df repolymer A) was obtained by reacting 360 parts of Df repolymer A with a terminal incyanate group content of 5.9 To (Df) under a nitrogen stream at 80°C for 5 hours.

(Adjustment of compound B) 100 parts of PPT with an average molecular weight of 3000, average molecular weight 2
000 PPG 100 parts, average molecular weight 4000PPT
52 parts, dibutyltin dilaurate 0.4 parts, N-dimethyllacrylamine 1.6 parts, water (foaming agent) 1 part, polymethyl ziraud? ? A mixture of 5 parts of a foam stabilizer and 280 parts of calcium carbonate (trade name MS-200, manufactured by Nitto Funka Kogyo Co., Ltd., hereinafter abbreviated as Charcoal) was mixed to obtain a composite material B.

(Adjustment of Compound C) Does it contain methylenebis(0-chloroaniline)? Reamin (Product name: Ki, 7min ML manufactured by Ihara Chemical Co., Ltd.)
-520) 30 parts, DOP 30 parts, t/f lead fluorate (2
0 wt% PB content) 2 parts, red iron 7 parts, charcoal
Compound C was obtained by mixing 31 parts.

Example-l As a polyurethane resin layer, 50 parts each of Gredelymer A and Konnoyoshiundo B, and polystyrene peas (particle size 0
．． 6-0.9101, manufactured by Dainippon Ink and Chemicals Co., Ltd.
5 parts of the product (trade name: 50K) were added, stirred and mixed, and the mixture was applied to a thickness of about 2H using a metal trowel. Unsaturated polyester resin (manufactured by Dainippon Ink & Chemicals Co., Ltd., Polylye) as an FRP layer on the polyurethane resin layer after curing
FR-200) was applied, and on top of that, FRP layer (A50P/m'', manufactured by Nittobo Co., Ltd.) was laid to form an FRP layer with a thickness of approximately 1.5B.The resulting composite coating structure Table 1 shows the physical properties of the body.

Comparative Example-1 A coating layer made of foamable polyurethane resin alone, which is the lower layer of Example 1, was created in the same manner as Example-1. The results are shown in Table-1.

Comparative Example-2 The upper layer of Example-1 was a coating layer made of FRP alone.
Created in the same way. The results are shown in Table-1.

Example-2 As a polyurethane resin layer! 50 parts each of Repolymer A and Congukundo C and polystyrene peas (particle size 1.
3-1.80φ, Dainippon Ink Chemical Products, Lie 7
10 parts of 4 mm Lua (0K) was added, stirred and mixed, and the mixture was applied to a thickness of about 2 flI using a metal trowel. After curing I urethane resin layer K Vinyl ester resin as FRP layer (Dainippon Ink Kagaku Kogyo Nashi, Diclite UE-3
505) and A50iP/ln
An FRP layer having a thickness of approximately 1.5'B was formed by using a material manufactured by Nittobo Co., Ltd.).The physical properties of the resulting composite coating structure are shown in Table 1.

Example-3 Same polyurethane resin K as Example-1, butadiene/
Five parts of styrene copolymer beads (particle size 0.8 to 1.2+n) were added to form the same FRP layer as in Example 1 as the upper layer. The physical properties of the obtained composite coated structure are shown in Table IK.

Comparative Example 3 In Example 1, a composite covering structure was formed in which the lower layer was made of a foamable polyurethane resin without adding polystyrene beads, and the upper layer was made of the same FRP as in Example 1. The physical property values are shown in Table-1.

Comparative Example 4 In Example 2, a coating layer was created using only a non-foaming 4-urethane resin layer without adding polystyrene beads. The physical property values are shown in Table-1.

Comparative Example-5 100 parts K of the same polyurethane resin as in Example-1 and 5 parts of polystyrene beads with a particle size of 0.1 to 0.3111 (manufactured by Dainippon Ink Co., Ltd., Lienol 30K) were added, and the An FRP layer similar to that in Example-1 was formed. Table 1 shows the physical properties of the composite coated structure obtained.

Example-4 Acrylic resin granules (particle size 3n manufactured by Mitsubishi Rayon Co., Ltd., Diamond Beads Resin BR-
100) was mixed and a composite coated structure was obtained in the same manner as in Example-1. The results are shown in Table-1.

Example-5 100 parts of the same polyurethane resin as in Example-1 was applied onto a glass plate substrate in an amount of 2 to 9 parts m'', and I-lyester-based granules (particle size 3xx (ret, Toagosei Chemical Co., Ltd.) PES-110H manufactured by Co., Ltd.) at 0.5 kll/ln”
Spread. After curing the urethane, a 1 xx thick FRP plate was placed in a 130° C. flat plate mold, and molded at 100° C. and a pressure of 5 days to obtain a composite coated structure. JISA69
The interlayer adhesion strength according to No. 10 was 6.2 kg/an''.

Example-6 In the same manner as in Example-4, 0.5 kg of EVA-based granules having a diameter of 2 m and manufactured by Orion Kasei Co., Ltd., Oritac P-110) was sprinkled onto a polyurethane resin. And example-
A structure was obtained in the same manner as in 4. The interlayer adhesion strength according to JISA6910 is 3.6 kg/c-9.

[Brief explanation of the drawing]

Figure 1 shows the back vapor pressure tester used for the blister generation test.
・Test piece, 4...Rubber, 5...Seal stamping,
6...Top lid, 7...S(-sir), 8...Pressure gel, FIG. 2 is one embodiment of the structure of the present invention.9.
...Base, 10... Brimer layer, 11... Polyurethane resin layer, 12... Granular material, 13... Fiber-reinforced thermosetting resin. Agent Patent Attorney Katsutoshi Takahashi Figure 1 Back vapor pressure tester Figure 2

Claims (1)

[Scope of Claims] 1. A composite covering structure consisting of (A) a fiber-reinforced thermosetting resin layer, (B) a polyurethane resin layer containing plastic particles with a diameter of 0.4 mm or more, and (C) a substrate. 2. A civil engineering building, characterized in that the structure according to claim 1 is used as a waterproof layer. 3. A characteristic feature is that plastic particles with a diameter of 0.4 mm or more are applied on the substrate (C) so that they are visible on the surface of the polyurethane resin layer (B), and then the fiber-reinforced thermosetting resin layer (A) is provided. Structure construction method.