JP3446261B2 - Composite covering structure, civil engineering building and composite covering structure construction method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite coating structure, a civil engineering structure using the composite coating structure as a waterproof layer, and a method for constructing a waterproof composite coating structure.

More specifically, it is used for various civil engineering structures such as a structure based on asphalt, concrete or mortar, or a structure based on a metal driving body. Composite coating structure with excellent skin resistance), adhesive strength, crack followability, waterproofness, impact resistance, dent resistance, fatigue resistance, integrity with the vehicle body, civil engineering construction using it as a waterproof layer The present invention relates to a method of constructing a composite covering structure for buildings and civil engineering structures.

[0003]

2. Description of the Related Art A composite coating structure using a concrete structure or a metal precursor as a base has an elongation of 30 on the base.
% Of the polymer composition layer, the adhesive layer for the fiber-reinforced thermosetting resin layer, and the fiber-reinforced thermosetting resin layer have been proposed by the present inventors. (JP-A-3-2
This is a coating structure in which a polyurethane resin layer or an asphalt / emulsion layer and an FRP layer are combined with an adhesive.
This structure has improved salt barrier properties, scratch resistance, and carbon dioxide gas barrier properties.

Generally, a waterproof material applied when waterproofing is formed even when various low-speed and high-speed expansion / contraction motions and cracks occur on the base material ground of civil engineering buildings. The waterproof layer itself is required to have excellent stretchability or adhesive strength, and further excellent durability, so that cracks and peeling are not easily caused.

However, the waterproof layer formed by the FRP-based covering structure generally has a problem of poor crack followability,
For this reason, stress concentration points occur at joint cut portions at so-called regular intervals in rooftop waterproofing of civil engineering buildings, which easily leads to breakage. Further, even if a waterproof coating is applied on top of that, there still remains a problem that cracks easily occur.

The composite coating structure disclosed in Japanese Patent Laid-Open No. 3-261547 is further improved and improved, in particular, in the follow-up property, waterproof property, salt barrier property, scratch resistance, carbon dioxide gas barrier property and the like. . However, when using the asphalt emulsion composition, there were the following problems.

(1) In the case of a coating type asphalt emulsion, swelling due to water is likely to occur and there is a problem in its strength. In other words, the asphalt emulsion itself is a one-pack type, so it is excellent in handleability and is also excellent as a flexibility-imparting lower layer waterproofing material. There are advantages such as no danger of.

[0008] The greatest advantage of using an asphalt emulsion is that it is significantly cheaper than other polymeric composition waterproofing materials, but this material has a unique viscoelasticity. It is in the place of possessing properties. That is, even if a breakage occurs in the asphalt waterproof material layer due to a large movement of the civil engineering building structure, the temperature rises in the summer, the viscous property becomes stronger, and the breakage naturally becomes self-adhesive. This is because the property is held.

However, on the principle of evaporating water to form a coating film, there is a drawback in workability that the drying and curing time becomes long and the construction time is long. In particular, due to the relationship with the film-forming temperature, the drying and curing time is significantly extended in winter (the curing and drying property is poor). On the other hand, in the summer, due to the high temperature, only the surface of the coating film is dried and becomes a skin-tight state, and the moisture inside the coating film is trapped, which prevents the film from drying. . That is, these problems lead to a fatal defect of blistering of the waterproof material. Moreover, the maximum coating thickness is 0.
Since the limit is 5 mm, the asphalt emulsion is unsuitable as a flexible layer of the composite coating structure in terms of coating film thickness.

That is, as described above, in the case of asphalt emulsion, when this is applied to an object and a film is formed, it is necessary to remove water by evaporation, and it is necessary to use it at a low temperature, in a sealed state or in a laminated state. When used or applied thickly, the formation of a dry film on the surface is significantly delayed, and in some cases it cannot be put to practical use. In addition, in the case of thick coating, unevenness of the drying rate within the layer causes nonuniformity of the film such as generation of cracks. In order to prevent such problems, the formation of a film is promoted by adding an emulsion destroying agent such as sodium fluorosilicate or a metal salt. However, in this method, it is still necessary to evaporate and remove the water generated by the emulsion breakage, and the water and water-soluble components generated by the emulsion breakage are extruded to the film surface and the underlayer interface, which significantly impairs the water resistant adhesive strength. At the same time, it causes blistering.

(2) There has been no adhesive having an excellent adhesive strength which can be used when the asphalt emulsion layer and the fiber reinforced thermosetting resin (FRP) layer are combined and bonded. That is, generally, as the adhesive for asphalt composition, hot melt asphalt, asphalt emulsion, and the like, which are based on asphalt or modified asphalt which is a homogeneous material, are used. The reason for using this is that since various solvents are mixed in these general-purpose adhesives, the phenomenon of cutting back asphalt occurs, resulting in a significant decrease in adhesiveness, Is almost unusable. As a special case, an epoxy resin may be used by taking advantage of characteristics such as good adhesiveness and high mechanical strength. However, in general, epoxy resin
In order to use various plasticizers, reactive diluents, and the like as a flexibility-imparting agent from the place of poor flexibility, these materials are
During long-term exposure, it scatters and loses its flexibility, resulting in poor adhesion. Furthermore, due to the long curing time,
The construction productivity is poor, and particularly during winter, the construction becomes extremely hard at 5 ° C. or less.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide a composite coating structure using a fiber reinforced thermosetting resin composition (referred to as FRP) waterproof material having excellent strength and physical properties as an upper waterproof material, and asphalt as a lower waterproof material. -Problems when using an emulsion composition, that is, curing and drying properties of the asphalt-emulsion composition during thick coating, coating surface drying property (skin resistance) and workability, asphalt-emulsion composition and the FRP It is intended to improve the adhesive strength with the layer and improve the followability and strength performance of the composite coated structure.

[0013]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies on the above problems and, when compounding an FRP waterproof material, use an asphalt emulsion composition containing a hydraulic silicate for curing and drying. In addition, when fiber material (C) is used for construction at high temperature in summer, surface dryness (skin resistance) and adhesion strength with FRP waterproof material are improved, dent resistance, impact resistance, fatigue resistance It was found that an excellent composite coating structure can be obtained, and the present invention has been completed.

That is, the present invention uses the fiber-reinforced thermosetting resin composition as the upper waterproof material (A) from above .
There layer (B) layer using a fiber-reinforced thermosetting resin composition layer adhesive layer using the (C) fibrous material layer (D) asphalt emulsion composition containing a hydraulic silicate as a lower waterproof material ( The adhesive layer according to claim 1, wherein E) a composite coating structure having a primer layer (F) substrate, and further (A) an upper waterproof material.
Fiber-reinforced thermosetting resin composition using resin for (B) is used
It provides a laminar (C) fibrous material layer (D) lower waterproof material as a layer with asphalt emulsion composition containing a hydraulic silicate (E) a primer layer (F) composite cladding structure having a substrate Is.

Further, the (D) layer of the asphalt emulsion composition containing a hydraulic silicate is characterized by comprising a rubber-asphalt emulsion, a hydraulic silicate and an adhesive resin. Composite coating structure.
The fiber material of the layer (C) is a fiber reinforced material, glass fiber,
Alternatively , a composite coating structure characterized by being an organic fiber . The thermosetting resin composition in which the adhesive for the (B) layer comprises (a ) a vinyl ester resin, (b) an air-drying imparting polymer, and (c) an ethylenically unsaturated monomer having an acryloyl group or a methacryloyl group. The present invention provides a composite coating structure, which is a product, and a civil engineering building in which the composite coating structure is a waterproof structure. Further, a primer layer (E) is applied on the substrate (F), and then a lower layer is formed thereon.
A layer (D) using an asphalt emulsion composition containing a hydraulic silicate as a waterproof material was applied, then a fiber material layer (C) was applied thereon, and a fiber-reinforced thermosetting resin composition was used. The present invention provides a method for applying a composite coating structure, which comprises applying an adhesive layer (B) for layers, and further applying a layer (A) using the fiber-reinforced thermosetting resin composition thereon. .

(Structure) The present invention will be described in detail below.

[0017] Using a fiber-reinforced thermosetting resin composition of the present invention
The thermosetting resin used in the layer (A) is an unsaturated polyester resin, a vinyl ester resin, an epoxy resin, a phenol resin or the like, preferably an unsaturated polyester resin or 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. Is obtained by dissolving 30 to 80 parts by weight of an unsaturated polyester produced by using an aliphatic or alicyclic saturated dibasic acid as an acid component in 70 to 20 parts by weight of an α, β-unsaturated monomer. Some of them are listed. The vinyl ester resin is a resin obtained by vinyl-modifying the end of an unsaturated polyester and a resin obtained by vinyl-modifying the end of an epoxy resin skeleton. If necessary, a curing agent, a curing accelerator, a filler, a thickener, a low-shrinking agent, etc. are added to these.
In particular, addition of a curing agent and a curing accelerator is useful.

The curing agent acts on unsaturated polyester resin, vinyl ester resin, etc., and is, for example,
Azo compounds such as azoisobutyronitrile, tertiary butyl perbenzoate, tertiary peroctoate, benzoyl peroxide, methyl ethyl ketone peroxide, organic peroxides such as dicumyl peroxide, and the like, and unsaturated polyester Usually, it can be used in the range of 0.3 to 3 parts by weight with respect to 100 parts by weight of the resin.

As the curing accelerator, that is, as a substance having a function of decomposing an organic peroxide as a curing agent by a redox reaction and facilitating generation of an active radical, a cobalt-based, vanadium-based or manganese-based substance is used. Such as various metal soaps, tertiary amines, fourth
Particularly, a typical ammonium salt or a mercaptan is used.

[0021] The fiber reinforcement used to reinforce a thermosetting resin, for example, glass fibers, amides, Ara Mi de, vinylon, polyester, organic fiber such as phenol, carbon fibers, metal fibers, ceramic fibers or their It is a combination. Considering workability and economy, glass fiber and organic fiber are preferable. The form of the fiber can be plain weave, satin weave, matte, etc.
The mat shape is preferable in terms of maintaining the thickness. It is also possible to cut glass roving into 20 to 100 mm and use it as chopped strands.

As the filler, calcium carbonate powder, clay, alumina powder, silica powder, talc, barium sulfate, silica powder, glass powder, glass beads, mica, aluminum hydroxide, cellulosic, silica sand, river sand, cold water stone, Known materials such as marble dust and crushed stone are mentioned, and among them, glass powder, aluminum hydroxide, barium sulfate and the like are preferable because they give semitransparency upon curing.

The layer adhesive using the fiber-reinforced thermosetting resin composition used in the layer (B) of the present invention is an adhesive which can be applied in a liquid form. Preferably, the composition is (a) vinyl ester resin, (b)
A thermosetting resin composition comprising an air-drying imparting polymer and (c) an ethylenically unsaturated monomer having an acryloyl group or a methacryloyl group.

The vinyl ester resin can be used not only as an adhesive layer but also as a resin for the fiber reinforced thermosetting resin layer (A) as described in claim 2.

The vinyl ester resin (a) is preferably referred to as a saturated or unsaturated polyester (meth) acrylate in the form of an addition reaction of the terminal carboxyl group of the saturated or unsaturated polyester with an unsaturated glycidyl compound. Is referred to as an epoxy acrylate obtained by reacting the end of the epoxy skeleton (epoxy resin) with α, β-ethylenically unsaturated dibasic acid in an equivalent ratio of 1: 2. These may be used alone or in combination of two or more.

The polyester (meth) acrylate resin is a saturated or unsaturated polyester having at least one (meth) acrylic acid ester group in one molecule,
Alternatively, it means a mixed solution of the (meth) acrylic acid ester group-containing (un) saturated polyester and polymerizable unsaturated monomers.

Here, the (un) saturated polyester is a polybasic acid (polycarboxylic acid) having a glycol component as a main component, a triol component as a polyol, and a dibasic acid mainly as a tribasic acid component. Refers to those obtained by the ester reaction with. In that case,
If necessary, a monoepoxide compound, an epoxy compound and / or an isocyanate compound may be used in combination.

As glycols for preparing the (un) saturated polyester, only typical ones are listed. Ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, hexylene glycol, dimethylolcyclohexane, 2, 4,4
-Alkylene glycols represented by trimethyl-1,3-pentanediol and the like;

Polyalkylene glycols represented by diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol and polyethylene glycol; dihydric phenols represented by bisphenol A, bisphenol F, bisphenol S and tetrabromobisphenol A. , An addition reaction product with an alkylene oxide typified by ethylene oxide and propylene oxide.

Specific examples of the triols are glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, etc., if only typical ones are listed.

As the tetraol unit, pentaerythritol, diglycerol, 1,2,3,4-butanetetriol and the like are particularly representative.

Further, only representative dibasic acids (anhydrides) are listed, o-phthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,
Tetrachlorophthalic acid, tetrabromophthalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, 1,1,2
-Dodecanoic acid, maleic acid, fumaric acid, itaconic acid, hymitic acid or het acid, etc., and if only particularly representative tribasic acid units are listed, trimellitic acid, aconitic acid, butanetricarboxylic acid Acid or 6-carboxy-3-methyl-1,2,3,6-hexahydrophthalic acid and the like, and as the tetrabasic acid unit, pyromellitic acid, butanetetracarboxylic acid and the like are particularly typical. is there.

As the monoepoxide unit, only representative ones are listed. Ethylene oxide,
Examples include propylene oxide, epichlorohydrin, styrene oxide, and phenylglycidyl ether.

A so-called epoxy resin can be preferably used as the epoxy compound, and one example thereof is plastic material course 1 "epoxy resin" (May 10, 1911, Nikkan Kogyo Shimbun). Published by Kuniyuki Shiramoto), pp. 19-48.

As the isocyanate compound unit, a polyvalent isocyanate compound known in the polyurethane industry can be preferably used, and one example thereof is the plastic material course 2 “Polyurethane resin” (Showa 44).
(Published by Nikkan Kogyo Shimbun, June 30, 2013, by Keiji Iwata)
Polyvalent isocyanate compounds as described on page 46, as well as pages 175-178.

The above-mentioned resin can be produced by an esterification reaction of a divalent, trivalent or tetravalent glycol with acrylic acid and / or methacrylic acid and a polybasic acid, or a (meth) acrylic group and a hydroxyl group. And a method of using an esterification reaction of a compound having

The unsaturated polyester is, for example, α,
produced by polycondensation reaction of β-ethylenically unsaturated dibasic acid or acid anhydride thereof, aromatic saturated dibasic acid or acid anhydride thereof, and glycols, and optionally, as an acid component, fat Examples thereof include those produced by using a group or alicyclic saturated dibasic acid together.

As the above α, β-unsaturated dibasic acids or their acid anhydrides, only typical ones are listed. Maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid or Examples include chloromaleic acid and esters thereof.

To list only particularly representative aromatic saturated dibasic acids or their acid anhydrides,
Phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride or halogenated phthalic anhydride, or esters thereof, etc., which are aliphatic or alicyclic. Specific examples of the saturated dibasic acid are oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid or hexahydrophthalic anhydride, or their esters. And each may be used alone or in combination of two or more.

Specific examples of glycols are only ester glycols, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol and 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 or 2,2-di- (4-hydroxypropoxydiphenyl)
Propane and the like may be used alone or in combination of two or more kinds, but in addition to them, an adduct with ethylene oxide, propylene oxide or the like may be similarly used.

Polyglycols and polycondensates such as polyethylene terephthalate can also be used as a part of the acid component.

As the unsaturated glycidyl compounds, only representative ones are listed. Glycidyl esters of various unsaturated monobasic acids such as acrylic acid or methacrylic acid, for example, glycidyl acrylate or glycidyl methacrylate. Is.

It should be noted that, as the unsaturated glycidyl compound, only representative ones are glycidyl acrylate and the like. Among them, it is preferable to use this glycidyl acrylate.

The number average molecular weight of the unsaturated polyester acrylate is preferably 1,500 to
3,000, particularly preferably in the range of 1,800 to 2,800 is suitable. When the molecular weight is less than 1,500, the obtained cured product is inevitably tacky or the strength properties are deteriorated. On the other hand, when it is greater than 3,000, the curing time is inevitably long. Productivity will be inferior.

The epoxy acrylate resin used in the present invention is, for example, a bisphenol type epoxy resin alone, or a combination of a bisphenol type epoxy resin and a novolac type epoxy resin. An epoxy vinyl ester obtained by reacting an epoxy resin having an average epoxy equivalent of 150 to 450 with an unsaturated monobasic acid in the presence of an esterification catalyst. Is.

Here, to mention only representative ones of the above-mentioned bisphenol type epoxy resins, epichlorohydrin and bisphenol A will be given.
Or obtained by reaction with bisphenol F,
A glycidyl ether type epoxy resin having substantially two or more epoxy groups in one molecule;

Or a dimethylglycidyl ether type epoxy resin obtained by the reaction of methyl epichlorohydrin with bisphenol A or bisphenol F; or an epoxy obtained by the reaction of an alkylene oxide adduct of bisphenol A with epichlorohydrin or methyl epichlorohydrin. Resin, etc.

Further, only the typical novolak type epoxy resins mentioned above are epoxy resins obtained by reacting phenol novolac or cresol novolac with epichlorohydrin or methyl epichlorohydrin. .

Further, to list only particularly representative unsaturated monobasic acids mentioned above, acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, sorbic acid,
Examples include monomethylmalate, monopropylmalate, monobutylmalate, or mono (2-ethylhexyl) malate.

These unsaturated monobasic acids may be used alone or in combination of two or more. The reaction between the above-mentioned epoxy resin and unsaturated monobasic acid is preferably 60 to 14
It is carried out with an esterification catalyst at a temperature of 0 ° C., particularly preferably 80 to 120 ° C.

As the esterification catalyst, known and commonly used compounds can be used as they are, but if only representative ones are listed, triethylamine,
Various tertiary amines such as N, N-dimethylbenzylamine, N, N-dimethylaniline or diazabicyclooctane; or diethylamine hydrochloride.

The number average molecular weight of the epoxy acrylate resin is preferably 900 to 2,500,
The range of 1,300 to 2,200 is particularly preferable. When the molecular weight is less than 900, the obtained cured product becomes sticky or the physical properties are deteriorated, while when it is more than 2,500, the curing time becomes long. , Productivity will come to decline.

The above-mentioned ethylenically unsaturated monomer (ha) having a (meth) acryloyl group used in the present invention is an unsaturated monomer capable of undergoing a crosslinking reaction with the above-mentioned vinyl ester resin (a). Unsaturated oligomers and the like can be mentioned as typical ones,
Above all, the use of (meth) acrylic acid ester monomers is desirable.

Any such (meth) acryloyl group is
If the monomers not used are used and the amount used is too large, the copolymerizability with the vinyl ester resin will inevitably deteriorate, and as a result, the disadvantage of longer curing time may occur. Become.

Specific examples of the (meth) acryloyl group-containing ethylenically unsaturated monomer include only methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and the like. T-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, decyl acrylate, acrylate 2
-Hydroxyethyl, 2-hydroxypropyl acrylate, β-ethoxyethyl acrylate, acrylic acid 2
-Cyanoethyl, cyclohexyl acrylate or diethylaminoethyl acrylate,

Alternatively, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, 2-hydroxyethyl methacrylate or methacrylate. 2-hydroxypropyl,

Alternatively, it may be phenylcarbitol acrylate, noniphenylcarbitol acrylate, nonifenoxypropyl acrylate, N-vinylpyrrolidone, polycaprolactone acrylate, acryloyloxyethyl phthalate or acryloyloxysuccinate.

Further, as various derivatives of dicyclopentanediene, silicylcyclodecane or triazine which can improve the surface dryness of the cured resin,
For example, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, tricyclodecanyl acrylate, tricyclodecanyl methacrylate, tris (2-hydroxyethyl) isocyanuric acrylate and the like are particularly representative examples.

Needless to say, the copolymerizability during the crosslinking reaction is slightly inferior, but vinyl-based monomers other than these may be used in combination.

If only representative examples of such a monomer are given, styrene, vinyl acetate,
Allyl monomers such as vinyltoluene, α-methylstyrene, diallyl phthalate, diallyl isophthalate, triallyl isocyanurate, diallyl tetraprom phthalate; acrylonitrile, glycidyl methacrylate, n-methylol acrylamide-butyl ether,
Examples include so-called hard monomers such as n-methylol acrylamide or acrylamide.

In the present invention, an unsaturated alcohol or a polyfunctional unsaturated monomer may be used in combination.

First, the unsaturated alcohol refers to a compound having an acryloyl group and a hydroxyl group, and specific examples of the compound include 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, acrylic acid 2 -Hydroxyethyl or hydroxypropyl acrylate.

These compounds are used when the composition of the present invention is used as compared with those using asphalt.

Next, the above-mentioned polyfunctional unsaturated monomers are defined as compounds having at least two polymerizable double bonds in one molecule, and refer to the compounds. Above all, the wear resistance of the surface of the cured product,
It is preferably used for the purpose of improving scratch resistance, sliding resistance and chemical resistance.

Among them, particularly preferable compounds are polyfunctional (meth) acrylic acid ester monomers, such as ethylene glycol di (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, 1 , 3-butylene glycol di (meth) acrylate or 1,6-hexanediol di (meth) acrylate
Various alkanediol di (meth) acrylates such as acrylates;

Various polyoxyalkylene-glycol di (meth) acrylates such as dipropylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol di (meth) acrylate or polyethylene glycol (meth) acrylate. Kind; or

Divinylbenzene, diallyl phthalate,
Triallyl phthalate, triallyl cyanurate, triallyl isocyanurate, allyl (meth) acrylate, diallyl fumarate and the like are mentioned as particularly representative ones, and these may be used alone or in combination of two or more kinds, Of course.

The above-mentioned air-drying imparting type polymer (b) used in the present invention is to introduce an air-drying component (air-drying imparting component) as an essential component into unsaturated polyester or vinyl ester resin. The thing obtained by this is referred to.

Examples of the method for introducing the air-drying component into the unsaturated polyester or vinyl ester resin as the above-mentioned polymer to be crosslinked are as follows.

One of them is --O--C as a glycol component.
In this method, a compound having an allyl ether group represented by H ₂ —CH═CH ₂ is used in combination. Next, for the acid component,
In this method, a compound derived from a cycloaliphatic unsaturated polybasic acid or a derivative thereof is used in combination.

Further, there is a method in which a compound derived from dicyclopentadiene is used in combination, and a drying oil, an epoxy reactive diluent and the like are also used in combination.

Of these various methods, first, as the allyl ether group-containing compound, any known compound can be used. Among them, only representative ones can be used. Glycol monoallyl ether, diethylene glycol monoallyl ether,
Triethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether or polypropylene glycol monoallyl ether,

Or 1,2-butylene glycol monoallyl ether, 1,3-butylene glycol monoallyl ether, hexylene glycol monoallyl ether,
Octylene glycol monoallyl ether, trimethylolpropane monoallyl ether, trimethylolpropane diallyl ether, glycerin monoallyl ether, glycerin diallyl ether, pentaerythritol monoallyl ether, pentaerythritol triallyl ether, various kinds of polyhydric alcohols Examples include allyl ether compounds and various allyl ether compounds having an oxirane ring such as allyl glycidyl ether.

Next, as a glycol component which is also used in combination, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butynediol, 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 can be mentioned, and they may be used alone or in combination of two or more kinds.

Furthermore, other oxides such as ethylene oxide and propylene oxide can be used in the same manner. Also, as a part of the glycol component and the acid component,
Polycondensates such as polyethylene terephthalate can also be used.

Further, as mentioned above, tetrahydrophthalic anhydride, endomethylene, and tetrahydrophthalic anhydride can be mentioned as only representative examples of the compounds composed of various cyclic aliphatic unsaturated polybasic acids or their derivatives. Tetrahydrophthalic anhydride, Methyltetrahydrophthalic anhydride, α-
Terhinene-maleic anhydride adduct, rosin or ester gum.

When used in combination with these cycloaliphatic unsaturated polybasic acids or their derivatives, first,
As only α, β-ethylenically unsaturated dibasic acids or their acid anhydrides, only typical ones are exemplified, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chlormalein. Acids or their esters and the like. Then, only specific examples of aromatic saturated dibasic acids or their acid anhydrides are listed, and phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid can be mentioned. , Nitrophthalic acid, halogenated phthalic anhydride or esters thereof, and further, only representative examples of aliphatic or alicyclic saturated dibasic acids are exemplified, and oxalic acid, malonic acid,
Examples thereof include succinic acid, adipic acid, sebacic acid, aceraic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof. These may be used alone or in combination of two or more kinds.

Further, synthesized from glycol and acid,
A resin obtained by reacting a terminal carboxyl group of an unsaturated alkyd resin with a reactive monomer having a glycidyl group can also be used.

Examples of such glycidyl group-containing reactive monomers include glycidyl acrylate and glycidime methacrylate, to name but a few.

Further, β-PM which is cis-3-methyl-4-cyclohexene-cis-1,2-dicarboxylic acid and its anhydride (hereinafter abbreviated as β-PMAA).
AA unit compounds can also be used, but the compound refers to β-PMAA as described above, and these compounds are adducts of trans-piperylene and maleic anhydride, or the adducts thereof. The acid anhydride group therein is obtained by ring opening.

Further, particularly representative compounds having dicyclopentanediene include hydroxylated dicyclopentanediene.

Further, by exemplifying only typical drying oils, linseed oil, soybean oil, cottonseed oil,
Examples include various fatty oils such as coconut oil or peanut oil, and further reaction products of these fatty oils with polyhydric alcohols such as glycerin.

As the epoxy reactive diluent, a monoepoxy compound and a polyepoxy compound are particularly representative. Examples of the former include allyl glycidyl ether, n-butyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylic acid ester or "CARDURA E" (product of Shell Co., Netherlands), and the latter example. As for belonging, "Unox 206" (American Union
Carbide product), "Epicoat 812" [product of Dainippon Ink and Chemicals, Inc.], DGE (diglycidyl ether), and the like.

In the production of unsaturated polyester, vinyl ester resin and epoxy vinyl ester resin, a polymerization inhibitor is used for the purpose of preventing gelation and adjusting the storage stability or curability of the produced resin. Is recommended.

Typical examples of the polymerization inhibitor used here include hydroquinones such as hydroquinone, pt-butylcatechol or mono-t-butylhydroquinone; hydroquinone monomethyl ether or di-t-. Phenols such as butyl-p-cresol: quinones such as p-benzoquinone, naphthoquinone or p-toluquinone; and copper salts such as copper naphthenate.

In addition to the above-mentioned curing agent and curing accelerator, a thickener, a low-shrinking agent and the like may be added to the resin composition of the present invention. It is preferable to contain an agent.

Examples of the curing agent include organic peroxides. Specifically, known conventional ones such as diacyl peroxide type, peroxy ester type, hydroperoxide type, dialkyl peroxide type, ketone peroxide type, peroxyketal type, alkyl perester type or percarbonate type. Is used and is appropriately selected depending on the kneading conditions and the curing temperature.

The amount added is the amount usually used, preferably 1 part of the unsaturated polyester resin composition.
The amount is 0.01 to 4 parts by weight with respect to 00 parts by weight, and the various curing agents as described above may be used in appropriate combination.

A low shrinkage agent can be added to the unsaturated polyester resin composition used in the present invention for the purpose of reducing cure shrinkage. Examples of such a low-shrinking agent include thermoplastic resins, and of these, only typical ones are exemplified, such as methyl methacrylate ethyl methacrylate, butyl methacrylate, methyl acrylate or ethyl acrylate, acrylic acid or Various lower alkyl esters of methacrylic acid; homopolymers or copolymers of various monomers such as styrene, vinyl chloride or vinyl acetate; or

As described above, at least one of various vinyl monomers, lauryl methacrylate, isovinyl methacrylate, acrylamide, methacrylamide,
Hydroxyl alkyl-acrylate or -methacrylate, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid or cetylstearyl methacrylate, such as a copolymer with at least one kind of various monomers,

Further, cellulose acetate butyrate or cellulose acetate propionate or polyethylene or polypropylene, or saturated polyester is used.

The fibrous material of the layer (C) of the present invention may be any as long as it has an effect of preventing surface dryness (skin burr resistance) when the asphalt emulsion is applied at high temperatures such as in summer. Further, it has the effect of reinforcing the asphalt / emulsion layer in curing when wet, and the effect of improving the adhesive strength with the FRP layer (A).
˜450 g / m ² . Specifically can use fiber reinforcement, e.g., glass fibers, amides, Ara Mi de,
Organic fibers such as vinylon, polyester and phenol,
It is carbon fiber, metal fiber, ceramic fiber or a combination thereof. Considering workability and economy, glass fiber and organic fiber are preferable. The form of fiber includes plain weave, satin weave, matte, etc.,
Workability, layer using asphalt emulsion composition
Considering the anchor effect of the fiber to (D) , the mat-like shape is preferable. A nonwoven fabric of organic fibers is particularly preferable.

The layer (D) using the asphalt emulsion composition containing the hydraulic silicate of the present invention is specifically as follows. That is, asphalt
The emulsion composition preferably contains a rubber-asphalt emulsion and an adhesive resin, and is a composition in which a powder of hydraulic silicate is added and added at the time of use.

The rubber-asphalt emulsion of the present invention may be any of anionic, cationic and nonionic ones, but it is necessary that it has sufficient emulsion stability to carry out the coating operation by adding and mixing the hydraulic silicate. There is. As the rubber-rubber in the asphalt, there are natural rubber, styrene-butadiene copolymer rubber, butyl rubber, polybutadiene rubber, chloroprene rubber, acrylic rubber, ethylene-vinyl acetate copolymer and the like, but preferably styrene-
Butadiene copolymer rubber or carboxyl modified styrene-
Having a butadiene copolymer as a main component is excellent in terms of performance and economy as a rubber-asphalt emulsion solid layer.

Examples of the asphalt in the rubber-asphalt include natural asphalt, straight asphalt, blown asphalt and the like, and any of them can be used. The content of the rubber component in the rubber-asphalt is not particularly limited, but is preferably 5 to 50% by weight based on the total solid content of the rubber-asphalt emulsion in terms of performance.

The tackifying resin as a modifying compound improves the adhesion to a wet substrate where the strength of the asphalt emulsion is poor, and the flexibility at low temperature which is a characteristic of the asphalt emulsion reduced by the presence of cement. Anything is fine. That is, it is necessary that the compatibility with the rubber-asphalt is good, the adhesiveness with the rubber-asphalt is improved, and the film performance thereof is not significantly deteriorated. Specific examples include various natural resins, rosin derivative resins, coumarone resins, phenol resins, terpene resins, petroleum hydrocarbon resins, rosin derivative resins, etc., particularly rosin, hydrogenated rosin glycerin ester, C ₅
System and C ₉ based petroleum resins are preferred. The softening point of this adhesive resin is 150 ° C. or lower, and particularly 60 to 120 ° C.
Are preferred. A resin having a softening point higher than this has poor compatibility with rubber-asphalt, and it is difficult to maintain the performance of the rubber-asphalt coating over a wide temperature range. A small amount of organic solvent may be added to these.

The amount of the adhesive resin used is preferably 1 to 30 parts by weight, and more preferably 5 to 15 parts by weight, based on 100 parts by weight of the total of rubber and asphalt. The optimum amount of the adhesive resin varies depending on the rubber-asphalt composition, the type of resin, etc., but if it is less than 1 part by weight, the effect of adding the resin is not obtained.
If it exceeds 30 parts by weight, the flexibility of the rubber-asphalt film is impaired, the tackiness becomes too strong, and the original properties of the rubber-asphalt are lost.

The hydraulic silicate used in the present invention is preferably in the form of powder and has a particle size such that it can be easily added and mixed at the time of construction. Further, hydraulic silicates that generate more etrigite products at the end of the hydraulic reaction are preferable, but ordinary Portland cement, early strong portland cement, ultra early strong portland cement, moderate portland cement, jet cement, blast furnace cement, Silica cement, fly-ash cement, etc. can be used. When the hydraulic silicate powder is mixed with the rubber-asphalt emulsion to cure the rubber-asphalt emulsion, the hydraulic silicate powder should be uniformly dispersed in the rubber-asphalt emulsion and have sufficient fluidity during the construction work of the mixed composition. It is preferable that the composition has a property of coagulating and forming a cured film of the mixed composition as soon as possible after the construction. In order to achieve these required performances, the rapid hydraulic hardness is strong, and hydraulic silicate powder adjusted so as not to be condensed immediately after being dispersed in water, for example,
A cement silicate containing 10% by weight or more of each of Al ₂ O ₃ and SO ₂ is preferable as a chemical component that produces more ethrincheite products when the hydraulic reaction is completed.

The amount of the hydraulic silicate powder added is 20 to 150 parts by weight based on 100 parts by weight of rubber and asphalt in total. If the proportion of hydraulic silicate is more than the above range, the performance may be deteriorated, such as the risk of cracking of the formed film and the reduction of elongation. On the other hand, if the proportion of the hydraulic silicate added is less than the above range, the rubber-asphalt emulsion composition will slow to coagulate, free water will not be easily captured, and the curing and drying properties will be poor.

The asphalt emulsion composition comprises
Not only by evaporation and removal of water, but mainly by the internal retention of hydraulic silicate as crystal water, it has the ability to form a cured film, and maintains stable strength and elongation over a wider temperature range and curing conditions. In addition, the adhesion with the base can be improved.

There are various methods for producing the rubber-asphalt emulsion composition for the layer (D) , but the performance of the present composition is not greatly influenced thereby. As a manufacturing method, (1) a molten asphalt is emulsified, an aqueous emulsion is formed, and a rubber latex or an emulsion and a resin emulsion are added and mixed therewith to prepare a modified rubber-asphalt emulsion.
Mix hydraulic silicate powder. (2) Melt and mix rubber and resin in asphalt, homogenize it, and then make an aqueous emulsion with an emulsifier to produce a modified rubber-asphalt emulsion, and mix hydraulic silicate powder before use. (3) Molten asphalt is made into an aqueous emulsion with rubber latex or emulsion and an emulsifier, and then a resin emulsion is added and mixed to form a modified rubber-asphalt emulsion,
There is a method of mixing hydraulic silicate powder before use.

In these production methods, it is useful to use an organic solvent in the emulsification of the resin, the catalyst for the rubber and the asphalt of the resin, etc., and it is effective in imparting the tackiness of the rubber-asphalt and increasing the flexibility of the film. Is what you do. However, overuse of solvent is
In terms of performance, the amount used is preferably 30 parts by weight or less based on 100 parts by weight of rubber and asphalt in total.

Examples of the organic solvent include raw material monomers of the above vinyl ester resin and unsaturated polyester, the above ethylenically unsaturated monomer, ordinary solvents (xylene, toluene, vinyl acetate), alcohols, glycols. And the like.

The surfactant has become an important factor in the present composition. Emulsion stabilizer for rubber-asphalt emulsion, while maintaining sufficient emulsion stability of adhesive resin,
It is necessary to stably mix the hydraulic silicate powder and to impart stability to the coating area so that the spraying operation can be easily performed. However, in order to maintain the adhesion strength, water resistance strength, etc. of the formed film, it is desirable that the amount be as small as possible.

Examples of the surfactant include fatty acid salts, higher alcohol sulfates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkyl sulfonates, alkyl phosphate salts, polyoxyethylene sulphate salts, alkylamine salts, 4th group. Ionic surfactants such as primary ammonium salts and polyoxyethylene alkylamines, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers,
There are nonionic surfactants such as sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene amine ester, and oxyethyleneoxypropylene block polymer, which can be used alone or in combination. The amount of the surfactant used cannot be specified, but it must be limited to the required minimum amount. The type, amount, and time of use of the surfactant differ depending on the production method described above, but it is preferable to use a nonionic surfactant when adding the hydraulic silicate powder.

If necessary, various additives, antiaging agents, plasticizers, fillers, aggregates, thickeners, etc. can be added to the asphalt / emulsion composition of the layer (D). . In particular, the thickener is an additive necessary for adjusting and obtaining the viscosity required for coating.

Furthermore, in order to reduce the troweling workability of the layer (D) using the asphalt emulsion composition containing a hydraulic silicate and the temperature dependency due to heating, an aggregate such as silica sand should be mixed. Is extremely useful. The aggregate includes natural aggregate and artificial aggregate.

As the former, only typical examples are river gravel, river sand, mountain gravel, mountain sand, sea gravel or sea sand, while the latter is rock, clay or We refer to those processed from industrial by-products as raw materials, and if we only exemplify representative ones among them, crushed stone, crushed sand, silica sand,
It is slag crushed stone, crushed sand, or artificial lightweight aggregate. Further, the following filler may be used in combination with a part of the aggregate.

As the fillers, only representative ones are given as examples: calcium carbonate powder, clay, alumina powder, silica powder, talc, barium sulfate, silica powder, glass powder, glass beads, mica, and hydroxide. Examples thereof include known ones such as aluminum, cellulose yarn, silica sand, river sand, cold water stone, marble scraps or crushed stones. Among them, calcium carbonate, glass powder, aluminum hydroxide or barium sulfate is preferably used.

As a construction method, after a primer layer ( E ) is provided on a target substrate (base) (F) , a brush,
Apply with a trowel, or by applying an appropriate pump pressure, spray with an air gun or airless gun.
In the winter, if a heated hot air dryer is used, the film shape can be further promoted.

For the primer layer ( E ), known and commonly used primer compositions can be used. For example: That is, the standard specifications for construction work issued by the Architectural Institute of Japan
Synthetic resin-based sealer for base conditioning material described in 2.2 on page 8 of the same commentary (JASS23 spraying work). Alternatively, asphalt, synthetic rubber such as chloroprene, a resin composition such as acrylic, urethane, epoxy, polyester and the like solvent-based,
There it is those in aqueous, aqueous asphalt from compatibility with the above Symbol asphalt composition.

As the substrate ( F ) used in the present invention,
Particularly representative examples are cement concrete, asphalt concrete, JIS A-540.
3 (asbestos slate), ALC plate, PC plate, FRP, plastic, wood or metal, etc., which are configured alone or in combination, and the shape thereof may be any structure Any surface such as a spherical surface, a curved surface, an extended surface, a flat surface or an inclined surface may be used.

Usually, it is a plane or slope of cement concrete or asphalt concrete. For solid substrates such as concrete and metal, it is recommended to perform surface treatment or primer treatment if necessary.

The composite coating structure of the present invention is applied to the substrate of civil engineering and construction as follows, using the composition for forming the layers (E) to (A) described above. That is, a step of first applying a so-called primer on the substrate (F) can be mentioned. As such a primer, various kinds such as asphalt-based, urethane-based, epoxy-based or polyester-based can be used. Therefore, it is appropriately selected from the viewpoints of workability and substrate conditions.

After the primer is dried, the layer (D) using the asphalt emulsion composition containing hydraulic silicate is coated. As a method for mixing the asphalt emulsion composition, the hydraulic silicate, and optionally the aggregate, a known and commonly used method such as a mortar mixer is used. As a construction method, it is possible to apply by brush, trowel, rake or the like to the target substrate, or spray coating with an air gun or an airless gun by applying an appropriate pump pressure. The film shape can be further promoted by using hot air drying.

The placement of the fiber material forming the (C) layer as a measure for preventing blisters during construction in a high temperature atmosphere is performed in parallel with the construction work of the asphalt / emulsion waterproof layer in order to prevent blistering and improve the adhesive effect. While proceeding.

After the asphalt emulsion composition is dried and cured, an adhesive layer (B) containing a prescribed curing agent is applied. At this time, when the lower layer of the adhesive has a fiber material, the resin is impregnated into the fiber. As a construction method, a known and common method such as a hand lay-up method or a spray-up method may be used.

When the layer (A) using the fiber reinforced thermosetting resin composition is applied, it is generally applied while impregnating a glass mat with an unsaturated polyester resin or the like . As the construction method, the well-known and commonly used methods such as the hand lay-up method and the spray-up method may be used as described above.

In the present invention, a fiber-reinforced thermosetting resin is optionally used.
You may provide a surface layer together on the layer (A) using a fat composition . The "surface layer" used here is used in the form of applying various materials after applying the above-mentioned structure on a civil engineering building, depending on the purpose and application, to give various functions.

When it is used as a waterproof layer, a well-known and commonly used top-coating material such as a fluorine-based, acrylic-based, urethane-based or acrylic-silicone-based material having excellent weather resistance is applied on the piece to form a surface layer. Become.

When the waterproof composite covering structure for civil engineering and construction of the present invention is used as a parking lot, a playground or a rooftop garden, there are various construction methods for the surface layer. For example, a soil layer, a mortar layer, a non-slip layer, or the like is applied as a surface layer.

Of these methods for applying the surface layer, the preferred method for particularly heavy usage is a non-slip resin / aggregate or cement mortar / aggregate. The thickness is preferably 1 to 30 mm
The range of 3 mm to 15 mm is particularly preferable.

The above-mentioned resin / aggregate is a mixture of a filler and a resin, to which the aggregate is added. Preferably, the amount of the aggregate is 200 to 100 parts by weight of the resin.
The proportion is preferably 900 parts by weight, particularly preferably 3
It was added at a rate of 100 to 500 parts by weight.

When coloring in the present invention, the coloring agent is
Conventionally known organic and inorganic dyes and pigments can be used, but among them, those which are excellent in heat resistance and transparency and do not significantly disturb the curing of unsaturated polyester are preferably used.

The composite covering structure and the construction method of the present invention include road pavement, various bank structures such as bicycle races and auto races, roofs of buildings, rooftops, open corridors, etc. Alternatively, it can be used and applied as a balcony, outer wall, underground outer wall, waterproof membrane structure for indoors or aquariums.

In particular, outdoor waterproofing can be used for heavy walking waterproofing, parking lots, etc., because a person, a car, etc. can maintain sufficient durability even when riding on it. Also, since it has an effect on the followability of the base crack due to the asphalt layer,
As an earthquake-resistant structure, it can be greatly utilized and utilized in the fields of civil engineering or construction.

[0127]

EXAMPLES Next, the present invention will be described more specifically with reference to Reference Examples, Examples and Comparative Examples. In the text, all “parts” and “%” are based on weight unless otherwise specified. I shall.

Here, the experimental procedure and the results of various performance evaluation tests will be described. As the resin for the present invention, epoxy acrylate (VE-1) and saturated polyester acrylate (UPA-1) are used as a vinyl ester resin polymer (hereinafter abbreviated as VE resin), respectively; United (below,
This is abbreviated as air-drying resin. ), An air-drying imparting type unsaturated polyester (UPE-1) was prepared.

Synthesis Example 1 [Epoxy acrylate (VE
-1) Preparation Example] "Epiclone 1050" having an epoxy equivalent of 470 obtained by the reaction of bisphenol A and epichlorohydrin in a three-necked flask equipped with a thermometer, a stirrer and a condenser [Dainippon Ink and Chemicals, Inc. ) Epoxy resin] of 4,600 g (corresponding to 10 epoxy groups), 860 g of methacrylic acid (corresponding to 10 carboxyl groups), 1.36 g of hydroquinone and 10.8 g of triethylamine until 120 ° C. When the temperature was raised and the reaction was continued for 10 hours at the same temperature, a liquid epoxy acrylate having an acid value of 3.5, a double bond strength of 536 and a color number of 2 was obtained. . Hereinafter, this is abbreviated as "VE-1".

Synthesis Example 2 [Preparation Example of Saturated Polyester Acrylate (UPA-1)] 3 mol of diethylene glycol, 7 mol of triethylene glycol, 10 mol of orthophthalic acid and 50 ppm of toluhydroquinone were added to 200 to 20 mol. It was heat-condensed at ℃ and cooled to 140 ℃ when the acid value reached 28.

Then, 2 mol of glycidyl methacrylate was charged and reacted at 140 ° C. for 10 hours to obtain a target saturated polyester acrylate (UPA-1) having a double bond titer of 1,476.

Synthesis Example 3 [Preparation Example of Air-Drying-Providing Unsaturated Polyester (UPE-1)] 2 mol of β-PMAA, 2.5 mol of fumaric acid, and 5.25 mol of diethylenedalicol were used. Under a known condition, it is heated and dehydrated and condensed, and the double bond titer is 450.
Moreover, the target unsaturated polyester (UPE-1) having an acid value of 18 was obtained.

Synthesis Example 4 [Unsaturated polyester (UPE
-2) Preparation Example] 7 mol of orthophthalic acid, 3 mol of maleic anhydride, 3 mol of diethylene glycol and 7 mol of triethylene glycol and 50 ppm of toluhydroquinone are heated and condensed at 200 to 220 ° C, A control unsaturated polyester having a double bond titer of 838 was prepared. Hereinafter, this is abbreviated as UPE-2.

Synthesis Example 5 [Preparation Example of Asphalt Emulsion (As.Em)] Modified asphalt emulsion with styrene-butadiene copolymer having a concentration of 85% (composition ratio: styrene-butadiene copolymer / straight asphalt / water = 25
/ 35/30) 120 parts, polyoxyethylene alkyl ether-based surfactant (trade name: Emulgen 9
Stabilize by adding 15 parts of a 30% aqueous solution of 10.
Petroleum resin (trade name: Resin 90, Toho Petroleum Resin)
20 parts of 70% emulsion and a suitable amount of anti-aging agent were added and uniformly stirred with a stirrer to produce a modified asphalt emulsion.

Examples 1 to 6 and Comparative Examples 1 to 4 Various adhesive resin compositions were obtained according to the compounding ratios shown in Table 1.

<Test method><Test method for compatibility between adhesive resin and asphalt / emulsion composition> In order to evaluate compatibility between these adhesive resin composition and asphalt / emulsion waterproof layer, JIS S A peel adhesion test based on -6040 was performed.

The asphalt emulsion composition tested was asphalt emulsion 10 of Synthesis Example 5.
0 parts added with 50 parts jet cement,
This was applied on a concrete substrate in a thickness of 3 mm.
After curing at 20 ° C./65% for 12 hours, a test with an adhesive resin was carried out using two types, one with a fiber material applied thereon and the other with no fiber material applied.

The fiber material used had a basis weight of 80 g / m ^2.
It is a polyester non-woven fabric.

A peel adhesion test (hydraulic silicate-containing asphalt emulsion layer only) and a peel adhesion test (fiber material was applied on the hydraulic silicate-containing asphalt emulsion layer) were carried out, respectively. The results are summarized in Table 1.

In order to facilitate the peel adhesion test of the resin composition described above, a glass chopped strand of 450 g / m ² impregnated with the resin composition was used.

The compounding composition for curing is as follows: 100 PHR of resin, 2 PHR of BPO paste (50% solution), and 0.5 PHR of DMA. However, only in Comparative Example 3 using styrene, for 100 PHR of the resin, 1.0 PHR of MEKPO, 0.4 PHR of 6% cobalt naphthenate, and 0.1 PHR of DMA (dimethylaniline) were mixed and used. I was there.

<Method of Testing Surface Dryness of Asphalt / Em Composition> Two kinds of coating films were prepared on a glass plate at room temperature of 10 ° C. and 30 ° C. using an applicator to evaluate surface dryness. Then, a finger touch test was performed.

The evaluation method was carried out by measuring the time until the absorbent cotton does not remain on the surface of the coating film due to adhesion even if the absorbent cotton in an amount of about 2 to ³ cm ³ is pressed against the surface of the coating film. .

<Adhesion Test Method for Asphalt / Em Composition and Substrate> A uniaxial tensile adhesion test was carried out to evaluate the adhesiveness of the asphalt / Em composition depending on the type and condition of the base substrate. . When the test material is wet, the base substrate test body is dipped in water for one week, and immediately after being pulled up, it is applied on the test body in a thickness of 3 mm. The normal state was that the test body was cured at 20 ° C./65%, and then the test material was applied in the same manner as above. Application 2
After 4 hours, a uniaxial tensile adhesion test was performed. Adhesion test is 2
In a 0 ° C./65% atmosphere, a notch was made in the test material and a 40 mm × 40 mm steel jig was bonded using an epoxy resin agent. After the adhesive has hardened, a loading speed of about 1 kgf / cm2 is applied at 20 ° C using a hydraulic adhesion tester manufactured by Yamamoto Rakujuki Co., Ltd.
Tested in / sec. The base material is JIS concrete sidewalk plate (300 mm × 300 mm × 70 mm), dense grain ascon (300 mm × 300 mm)
mm x 60 mm).

The calculation method of the tensile adhesive strength is as follows.

<Test method for evaluation of blistering of asphalt / Em composition> About 2 mm on a slate plate (400 × 400 × 3 mm)
The material is applied, and the fiber material is placed on top of the applied material immediately after application. The sample was left in each constant temperature bath for 3 hours, and the number of blister occurrences was visually observed and evaluated.

[0147]

[Table 1] << Footnotes in Table-1 >> MMA …………………… Methyl methacrylate EMA …………………… Ethyl methacrylate HEMA …………… β-hydroxyethyl methacrylate

[0148]

[Table 2]

[0149]

[Table 3] << Footnote in Table-3 >>-cannot be measured because the coating surface is uncured

[0150]

[Table 4] << Footnotes in Table-4 >> 1. Unit (hr), x mark is not dry coating film.

[0151]

[Table 5] Table-5 Base condition and adhesive strength << Footnote of Table-5 >> Comparative Example-7 ---- JIS2 Class Urethane Waterproof Material Comparative Example-8 ---- Vinyl ester resin of Example-2

[0152]

[Table 6] Table-6 Blistering prevention effect when arranging fiber materials << Footnote of Table-6 >> 1) Evaluation criteria ○ ---- No abnormality △ ---- Slight occurrence × ---- Many occurrences on the whole surface 2) Kind of fiber material Fiber material 1-80g / m ² Polyester Non-woven fiber material 2--360 g / m ² glass mat fiber material 3-230 g / m ² glass cloth

Next, in order to make an evaluation focusing on the practicality as a roof waterproofing material, and particularly the performance evaluation as an exposure waterproofing method, the following Examples 18 and 19 will be given.
The composite coating structures of Comparative Examples 9, 10 and 11 were tested according to the “Test Method for Performance Evaluation of Membrane Waterproof Layer” of JASS “Waterproofing Construction” (1986) of the Japan Institute of Architecture, respectively.
The test was performed according to JIS A-1436 "Fatigue test of building materials for construction".

In order to focus on the performance evaluation as the exposure waterproofing method, the following three items were also tested. Indentation test A load of 45 kg is applied to the steel disc to check whether or not the waterproof layer breaks.

Impact resistance test A steel ball is dropped from a height of 1.5 m to check whether or not the waterproof layer breaks. The measurement was performed at an ambient temperature of 40 ° C.

Fatigue test A movement distance of 2.5 to 5 mm was repeatedly reciprocated 300 times (300 cycles) at a speed of 2 minutes / cycle to determine whether or not the waterproof layer was broken. I checked.
The measurement temperature was 20 ° C.

Example 18 The specifications of the asphalt waterproof layer were as follows. That is, the "dent test" for each of the three types of test pieces described above is the JIS A
A "fatigue test" consisting of a concrete slab as specified in 5304 is as follows: the asphalt primer of step 1 is applied to an asbestos slate plate of 8 mm size, then according to the compounding ratio of Example 9. The asphalt / emulsion composition was applied at a coating amount of 2 mm, 80 g / m ^{2 of} non-woven fabric was placed thereon, and an asphalt / emulsion waterproof layer was applied.

In the "impact resistance test", a waterproof layer was obtained by arranging and applying the asphalt emulsion composition and 80 g / m ² non-woven fabric without applying any primer.

Next, the adhesive resin (B) according to the compounding ratio of Example 2 was applied to each of the thus-prepared waterproofing layers so that the coating amount was 0.4 kg / m ² , and the resin was cured. It was

Then, to this, 0.4% of cobalt naphthenate and 1.2% of MEKPO were added to the unsaturated polyester resin "Polylite FR-200", and the mixture was stirred to give 450 g / m ² . FRP impregnated with one piece of chopped strand glass mat
By laminating and curing (A), a FRP thermosetting resin layer was formed on each of the waterproof layers, and used as a test body. The resin content of the impregnated product was 1.2 kg / m ² .

The results of the above-mentioned tests using this test body are summarized in Table 7.

Example 19 An asphalt emulsion layer was prepared in the same manner as in Example 18 except that the adhesive resin (B) according to the blending ratio of Example 2 was used instead of the unsaturated polyester resin. Specimens for the respective tests in which (D) and the fiber-reinforced thermosetting resin composition layer (A) (FRP layer) were formed were obtained.

The results of the above-mentioned tests using this test body are summarized in Table 7.

Comparative Example 8 The specification of the asphalt waterproof layer is JASS JAS JAS.
8 A test piece was obtained by performing steps up to step 8 of type A-PF described in Table 8.1.3 of "Waterproofing work" (1986).

The results of the above-mentioned tests using this test body are summarized in Table 7 below.

Comparative Example 9 A urethane waterproof layer was formed using the coating film waterproof layer type L-UF shown in Table 8.1.7 of JASS 8 “Waterproofing Work” (1986) above.

The reinforcing material step 5 of step 3 was omitted from the L-UF. Various tests were conducted also in the same manner as in Example 18. The results are summarized in Table-7.

Comparative Example 10 A cured product test body having only the thermosetting resin FRP layer of Example 18 was produced and tested in the same manner as in Example 18,
Collectively shown in Table-7.

[0169]

[Table 7]

Remarks). 1 Crack followability test A slate was used for the test substrate and a coating was provided on the slate to make a test sample, and Shimadzu Autograph (IS-5000) (Shimadzu Corporation)
Was used to measure the load-elongation curve. The evaluation was carried out by the load and elongation when the coating 2 provided on the substrate was broken or separated from the substrate.

2 Fatigue test Using a test piece, measurement was performed according to the fatigue test conditions (table) of the building construction standard specifications and the same explanation JASS8 waterproofing work (1986).
The testing machine used was a "hydraulic servo building finishing material fatigue tester" manufactured by Sagimiya Seisakusho.

[0172]

INDUSTRIAL APPLICABILITY According to the present invention, by using a composition in which a hydraulic silicate is mixed with an asphalt emulsion, the residual water content inside the coating film can be remarkably reduced, and the curing and drying property is improved, thereby providing an effect of preventing blistering. Moreover, in the summer, the temperature of the concrete surface to be constructed rises to nearly 60 ° C., so that the surface of the asphalt / emulsion layer undergoes a skin burr phenomenon in an extremely short time, leading to the formation of pout-like blisters. As a remedy for this, by disposing the fiber material (C) on the asphalt emulsion layer, the occurrence of surface skin burr phenomenon (skin resistance) can be improved.
Since it is disposed as an anchor in the asphalt / emulsion layer, it can contribute to the reinforcing effect of the asphalt / emulsion layer and the improvement of the adhesive strength with the FRP layer (A). Further, since the emulsion type composition is used, the workability is excellent even on the wet surface of the substrate.

Therefore, according to the present invention, it is possible to provide a useful composite coating structure for civil engineering, a civil engineering building, and a waterproof composite coating structural construction method thereof.
Due to the flexibility of the asphalt layer and the thermosetting resin composition layer or the fiber reinforced thermosetting resin composition layer, even if a crack occurs in the substrate such as concrete, cracks do not occur in these coating materials, and, By following the deformation of the substrate, so-called crack followability can be imparted.

In this way, even if the substrate is deformed,
It is possible to provide a composite coating structure that does not cause cracks, therefore has no water leakage, and can not only improve waterproofness, but also uses a thermosetting resin composition and is excellent in various other properties. Becomes

Claims (7)

(57) [Claims] 1. A fiber-reinforced thermosetting resin composition is used as the upper waterproof material (A) from above .
There layer (B) layer using a fiber-reinforced thermosetting resin composition layer adhesive layer using the (C) fibrous material layer (D) asphalt emulsion composition containing a hydraulic silicate as a lower waterproof material ( E) A composite coating structure having a primer layer (F) substrate. 2. The adhesive layer according to claim 1, as the upper waterproof material (A) from the top.
Fiber-reinforced thermosetting resin composition using resin for (B) is used
Laminar (C) fibrous material layer (D) lower waterproof material as a layer with asphalt emulsion composition containing a hydraulic silicate (E) a primer layer (F) composite cladding structure having a substrate. 3. The (D) layer asphalt emulsion composition containing a hydraulic silicate is a composition comprising a rubber-asphalt emulsion, a hydraulic silicate powder, and an adhesive resin. Claims 1 to 2 characterized by
The composite coating structure according to any one of claims. 4. The fiber material of the layer (C) is a fiber reinforcement material.
In the composite coating structure according to any one of claims 1-3, characterized in that the glass fibers or organic fibers. 5. The adhesive for the layer (B) is (a) a vinyl ester resin, (b) an air-drying imparting polymer and (c).
The composite coating structure according to any one of claims 1 to 4, which is a thermosetting resin composition comprising an ethylenically unsaturated monomer having an acryloyl group or a methacryloyl group. 6. A civil engineering building in which the composite coating structure according to any one of claims 1 to 5 is used as a waterproof structure. 7. A primer layer (E) is applied on a substrate (F), and then an asphalt emulsion composition containing a hydraulic silicate as a lower waterproofing material is used thereon ( D), then the fibrous material layer (C) thereon, the layer adhesive layer (B) using the fiber-reinforced thermosetting resin composition, and further fiber-reinforced thermosetting thereon. A method for applying a composite coating structure, which comprises applying a layer (A) using a resin composition.