JP2007245540A - Composite coating structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite coating structure free from interlayer separation and showing excellent crack following properties/waterproofness to a concrete and a mortar construction, a metallic driver, etc., and adhesion with the driver. <P>SOLUTION: This composite coating structure is formed of a coating layer obtained by fiber-reinforcing a heat-curable resin with a tensile elongation of not less than 90% at 23°C and an elastic modulas in tension of not more than 500 MPa by (A) JISK7113, (B) an adhesive layer for the fiber-reinforced heat-curable resin layer, (C) a polymer composition layer with not less than a tensile elongation of 30% by JISK6251, and (D) a base, laminated in that order from the top. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a composite covering structure applied to concrete and mortar structures and metal precursors.

The composite structure that is applied to concrete and mortar structures and metal precursors and has excellent crack-following properties, waterproofness, and adhesion to the precursors, is composed of fiber reinforced thermosetting resin and polyurethane resin layer. A composite covering structure is known (see, for example, Patent Document 1).
However, the above-described composite structure is excellent in crack followability, waterproofness, and adhesion to the fuselage, but the physical properties of the tensile elongation rate between the fiber reinforced resin layer and the polyurethane resin layer are greatly different. Trouble occurs. The main cause of peeling is thermal stress generated by each coating layer repeating thermal expansion and contraction.
Usually, when a composite covering structure is constructed on a roof, a rooftop, etc. for the purpose of protecting and waterproofing concrete and mortar structures, thermal expansion and contraction is repeated due to changes in environmental conditions such as daytime and nighttime, summertime and wintertime.
In order to solve this problem, a composite covering structure in which an adhesive layer is interposed between a fiber-reinforced thermosetting resin and a polymer composition resin layer having a high elongation rate has been proposed (see, for example, Patent Document 2). . Examples of the adhesive layer used in this structure include a one-part moisture-curing urethane primer, an epoxy primer, and an unsaturated polyester primer, and in any case, a fiber reinforced thermosetting resin layer and When the tensile properties of the polymer composition layer having a high elongation rate are greatly different, the strength of the adhesive is not sufficient, and peeling is observed between the two layers due to repeated thermal expansion and contraction.
JP-A-01-219242 Japanese Patent Laid-Open No. 03-261547

  An object of the present invention is to provide a composite structure that is free from delamination and has excellent crack followability, waterproofness, and adhesion to a precursor.

As a result of intensive studies to solve the above problems, the present inventor reduces the thermal stress generated between the polymer composition layer by specifying the tensile properties of the uppermost coating layer. As a result, it was discovered that peeling between the coating layer integrated with the adhesive layer and the polymer composition layer can be prevented, and the present invention has been completed.
That is, the present invention comprises: (A) a coating layer obtained by fiber-reinforced thermosetting resin having a tensile elongation of 90% or more at 23 ° C. and a tensile elastic modulus of 500 MPa or less as defined in JISK7113 (B) Fiber-reinforced heat An adhesive layer for a cured resin layer (C) A composite coating structure comprising a polymer composition layer (D) substrate having a tensile elongation of 30% or more as defined in JISK6251 is provided.

The composite covering structure of the present invention has no peeling between the coating layer and the polymer composition layer in which the thermosetting resin is fiber-reinforced, and when applied to concrete, mortar structure, metal precursor, cracks Excellent trackability, waterproofness, and adhesion to the fuselage.

Next, the present invention will be described in detail.
The tensile elongation specified in JISK7113 used for the layer (A) of the present invention is 90% at 23 ° C.
As described above, the thermosetting resin of the coating layer obtained by fiber-reinforced thermosetting resin having a tensile modulus of 500 MPa or less is unsaturated polyester resin, methacrylic resin, vinyl ester resin, epoxy resin, phenol resin, etc. Preferred are unsaturated polyester resins, methacrylic resins, and vinyl ester resins.

As unsaturated polyester resin, what melt | dissolved the well-known unsaturated polyester resin generally used conventionally by the well-known reactive unsaturated monomer can be used. The unsaturated polyester resin is obtained from an α, β-unsaturated carboxylic acid or an α, β-unsaturated carboxylic acid containing an optionally saturated carboxylic acid and an alcohol.
Examples of the α, β-unsaturated carboxylic acid include fumaric acid, maleic acid, maleic anhydride,
Examples thereof include itaconic acid, citraconic acid, mesaconic acid, chloromaleic acid, and dimethyl esters thereof. These α, β-unsaturated carboxylic acids may be used alone or in combination of two or more. Examples of the saturated carboxylic acid include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, hetic acid, hexahydrophthalic anhydride, adipic acid, sebacic acid, and azelaic acid. These saturated carboxylic acids may be used alone or in combination of two or more.

On the other hand, as alcohols, for example, ethylene glycol, diethylene glycol,
Propylene glycol, dipropylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,3-pentanediol, 1,6-hexanediol, cyclohexanediol, neopentylglycol, 2,2, 4-trimethyl-1,3-pentanediol, glycerin monoallyl ether, hydrogenated bisphenol A, 2,2-bis (4-hydroxypropoxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane Diols such as, triols such as trimethylolpropane, and tetraols such as pentaerythritol. These alcohols may be used alone or in combination of two or more.

Moreover, as a component of said well-known reactive unsaturated monomer, it is a monomer which has a liquid polymerizable double bond at normal temperature. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate And one or more (meth) acrylic acid esters selected from among (meth) acrylic acid esters. Furthermore, other polymerizable monomers, for example, (meth) acrylic acid ester having 1 to 12 carbon atoms, styrene, α-methylstyrene, (meth) acrylic acid amide, alkyl having 1 to 4 carbon atoms Mention may also be made of maleic acid esters and fumaric acid esters having a group, with styrene being particularly preferred.

Further, these reactive unsaturated monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, trimethylolpropane di ( It is also possible to use polyfunctional polymerizable monomers such as (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, hexanediol di (meth) acrylate, oligoethylene di (meth) acrylate, etc. it can.
The mixing ratio of the unsaturated polyester resin and the reactive unsaturated monomer is preferably unsaturated polyester resin: reactive unsaturated monomer = 40 to 80% by weight: 60 to 20% by weight.

As the methacrylic resin of the present invention, those obtained by dissolving a known polyester (meth) acrylate resin and urethane (meth) acrylate resin that have been conventionally used in general with the above-mentioned reactive unsaturated monomer can be used.
Examples of the polyester (meth) acrylate resin include saturated or unsaturated polyester having at least one (meth) acrylate group in one molecule, or (meth) acrylate group-containing (un) saturated polyester. It is done.

Moreover, the said urethane (meth) acrylate resin can be obtained by making a polyol, polyisocyanate, and a hydroxyl-containing (meth) acryl compound react.
Examples of the polyol include polyether polyols such as polypropylene oxide, polyethylene oxide, polytetramethylene glycol, bisphenol A ethylene oxide adduct, and bisphenol A propylene oxide adduct, polybutadiene diol, polyisoprene diol, polyester ether polyol, and polyester polyol. .
Polyisocyanates include 2,4-tolylene diisocyanate and its isomers or a mixture of isomers (hereinafter abbreviated as TDI), diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexyl. Mention may be made of methane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate and the like. Products include Barnock D-750, Crisbon NX (Dainippon Ink Chemical Co., Ltd. product), Death Module L (Sumitomo Bayer Co., Ltd. product), Coronate L (Nippon Polyurethane product), Takenate D102 (Takeda Pharmaceutical) Kogyo Co., Ltd. product), isonate 143L (manufactured by Mitsubishi Chemical Corporation), and the like. These can be used alone or in combination of two or more. Of the above polyisocyanates, diisocyanates, particularly TDI, are preferably used.

The hydroxyl group-containing (meth) acrylic compound is preferably a hydroxyl group-containing (meth) acrylic acid ester, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate; Mono (meth) acrylates of alcohols having two hydroxyl groups such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate; adducts of α-olefin epoxide and (meth) acrylic acid, glycidyl carboxylate Adduct of ester and (meth) acrylic acid; part of alcohol having 3 or more hydroxyl groups such as di (meth) acrylate of tris (hydroxyethyl) isocyanuric acid, pentaerythritol tri (meth) acrylate, etc. Acrylates, and the like.

In the production of the urethane (meth) acrylate of the present invention, a part of the hydroxyl group-containing (meth) acrylic compound is replaced with a compound such as a hydroxyl group-containing aryl ether or a higher alcohol within a range not impairing the effects of the present invention. May be.
As the hydroxyl group-containing aryl ether compound, known and commonly used ones can be used. Among them, typical ones include ethylene glycol monoaryl ether, diethylene glycol monoaryl ether, triethylene glycol monoaryl ether, polyethylene glycol monoaryl ether, Propylene glycol monoaryl ether, dipropylene glycol monoaryl ether, tripropylene glycol monoaryl ether, polypropylene glycol monoaryl ether, 1,2-butylene glycol monoaryl ether, 1,3-butylene glycol monoaryl ether, hexylene glycol mono Aryl ether, octylene glycol monoaryl ether, trimethylolpropane diaryl ether Glycerin diaryl ether, aryl ether compounds of polyhydric alcohols such as pentaerythritol triaryl ether and the like, aryl ether compounds having one hydroxyl group of these is preferred.

As the higher alcohol, known and commonly used ones can be used, but typical ones are decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol,
Examples include stearyl alcohol.

The urethane (meth) acrylate of the present invention first comprises a polyether polyol and a polyisocyanate, preferably a number average molecular weight of 500-30000, particularly preferably 700-.
It is made to react at NCO / OH = 2 to 1.5 so as to be 5000, to produce a terminal isocyanate group-containing urethane prepolymer, and then to the hydroxyl group-containing acrylic compound, the hydroxyl group is approximately equivalent to the isocyanate group of the prepolymer. It can obtain by making it react.
As another method for obtaining urethane (meth) acrylate, first, a hydroxyl group-containing acrylic compound and a polyisocyanate are reacted, and then the obtained isocyanate group-containing compound and a polyether polyol are reacted, preferably a number average. Molecular weight 500-300
00, more preferably 700 to 5000 urethane (meth) acrylates can be produced.

As the vinyl ester resin that is a thermosetting resin used in the layer (A) of the present invention, a known epoxy (meth) acrylate resin that has been conventionally used in general is dissolved in the above-mentioned reactive unsaturated monomer. Can be used. Examples of the vinyl ester resin include a bisphenol type epoxy resin alone or a mixture of a bisphenol type epoxy resin and a novolac type epoxy resin.
The vinyl ester resin is usually obtained by addition reaction of a terminal epoxy group of an epoxy resin and an unsaturated monobasic acid.
Examples of the bisphenol type epoxy resin include glycidyl ether type epoxy resin obtained by reaction of epichlorohydrin and bisphenol A or bisphenol F, and dimethyl glycidyl ether obtained by reaction of methyl epichlorohydrin and bisphenol A or bisphenol F. Type epoxy resin or an epoxy resin obtained from an alkylene oxide adduct of bisphenol A and epichlorohydrin or methyl epichlorohydrin.
Examples of the novolak type epoxy resin include an epoxy resin obtained by reaction of phenol novolak or cresol novolak with epichlorohydrin or methyl epichlorohydrin.

Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethylmalate, sorbic acid or mono (2-ethylhexyl) malate, and these unsaturated monobasic acids can be used alone, It is used even if 2 or more types are mixed. The mixing ratio of the epoxy acrylate resin and the reactive unsaturated monomer is preferably epoxy acrylate resin: reactive unsaturated monomer = 40 to 80% by weight: 60 to 20% by weight.

The adhesive layer (B) for fiber-reinforced thermosetting resin layer of the present invention is formed by coating with an adhesive that can be applied in a liquid state. Examples of the adhesive include urethane, epoxy, vinyl ester, unsaturated polyester, and acrylic. In consideration of on-site construction, a moisture curable urethane adhesive having an isocyanate group that reacts with moisture in the air is preferable.

Examples of the isocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, phenylene diisocyanate, 1,5-naphthalene diisocyanate, metaxylylene diisocyanate, water. Organic polyisocyanates such as hydrogenated tolylene diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, crude tolylene diisocyanate, polymethylene polyphenyl isocyanate, and the like can be used alone or as a mixture thereof.

Polyols are polyether polyols, polyester polyols, other polyols, and mixed polyols thereof. For example, a polyol produced using a double metal cyanide complex as a catalyst is also included.
Polyether polyols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylol propane, glucose, sorbitol, one or more polyhydric alcohols such as sucrose, propylene oxide, ethylene oxide, oxide. And polyols obtained by adding one or more of styrene oxide and the like, and polyoxytetramethylene polyols.

Examples of the polyester polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, glycerin, trimethylolpropane, and one or more other low molecular polyols, glutaric acid, adipic acid, Pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, hydrogenated dimer acid or other low-molecular dicarboxylic acids or oligomers with one or more condensation polymers, propiolactone, caprolactone And ring-opening polymers such as valerolactone.
Examples of other polyols include polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, and acrylic polyol. In addition, low molecular polyols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol glycerin, trimethylolpropane, glucose, sorbitol, and shoelace.

Both of these isocyanate and polyol components are converted into a urethane prepolymer through a known and usual urethanization reaction in such a ratio that the molecular ends become isocyanate. The urethane prepolymer is then diluted with a dilutable solvent to prepare a resin solution having a resin content of 10 to 70% by weight, preferably 15 to 50% by weight. As the solvents, usual urethane solvents such as toluene, xylene, terpene, and ethyl acetate can be used.

Examples of the polymer composition layer (C) having a tensile elongation of 30% or more as defined in JISK6251 for use in the present invention include a paint film-type resin composition layer and a sheet-like body. In the case of applying to a firm substrate such as metal, it is advisable to perform base treatment, primer treatment, etc. as necessary.
Examples of the sheet-like body include synthetic polymer roofing materials limited to JIS A6008.
The primer used between the substrate (D) and the polymer composition layer (C) is a generally known primer such as a one-component moisture-curing urethane primer, bisphenol A type epoxy /
A polyamine primer, an unsaturated polyester primer, etc. can be mentioned.
In the case where the polymer composition layer (C) having a tensile elongation of 30% or more is a sheet-like body, an adhesive is used for adhesion to the base. The adhesive is roughly classified into an organic solvent type and a non-organic solvent type, and there are an emulsion type and a two-component reaction type in which a main ingredient and a curing agent are used in a mixture, and none of them contains an organic solvent. This adhesive is used not only as a base and a sheet-like body, but also as an adhesive between the sheet-like bodies when a plurality of sheet-like bodies are used.

As the coating film type resin composition, when considering the crack followability of the substrate, JISA690, etc.
A multi-layer finish coating material specified in 9 or a roof waterproof coating material specified in JIS A6021.
Multi-layer finishing coating materials specified in JIS A6909 include polymer cement-based multi-layer finishing coating materials, synthetic resin emulsion (hereinafter referred to as “Em”) multi-layer finishing coating materials, and reaction-curable synthetic resin Em-based multi-layer finishing coating materials. Synthetic resin solution-based multi-layer finishing coating materials, waterproof synthetic resin solution-based multi-layer finishing coating materials, and the like.
The synthetic resin Em-based multi-layer coating material is an acrylic or vinyl acetate-based synthetic resin Em.
It is. The reaction curable synthetic resin Em is a reaction curable synthetic resin E such as an epoxy resin.
m. The synthetic resin solution-based multi-layer finishing coating material is prepared by dissolving a synthetic resin such as acrylic or vinyl in an organic solvent such as xylene or toluene, or a reaction-curable synthetic resin such as epoxy or urethane based on xylene, Dissolved in an organic solvent such as toluene.

Examples of the roof waterproof coating material defined in JIS A6021 include urethane rubber types 1 and 2, acrylic rubber type, chloroprene rubber type, acrylic resin type, and rubber asphalt type.
Urethane rubber series 1 and 2 are two-component urethane rubber waterproofing systems consisting of a main ingredient mainly composed of isocyanate group-containing compounds and a curing agent mainly composed of a crosslinking agent, a filler and the like. It is classified into 1 type and 2 type by the quality performance.
Here, the acrylic rubber type is an acrylic rubber Em type composition in which a filler or the like is blended with a non-vulcanized acrylic rubber whose main raw material is an alkyl acrylate.
An acrylic resin system is a composition which uses acrylic acid ester and methacrylic acid ester as main raw materials. The rubber asphalt system is a rubber asphalt Em composition containing asphalt and a rubber material such as styrene / butadiene or chloroprene rubber as main components. The chloroprene rubber system is a chloroprene rubber solution type waterproofing agent containing chloroprene as a main raw material and blended with a filler.
The rubber asphalt type is a rubber asphalt emulsion type waterproofing agent containing asphalt and rubber as main components.
Among these, those containing a urethane rubber system specified in JIS A6021 are preferable in terms of concrete protection and waterproof performance.

In addition to the resin, the coating film type resin composition includes an aggregate, a viscosity stabilizer, a nonionic surfactant, an antifoaming agent, an antifreezing agent, a dispersing agent, a wetting agent, an antiseptic, and a pH adjusting agent as necessary. , A thickener, a film-forming aid, various fillers, pigments, cement, fibrous materials, etc. may be partly or fully blended. When powders such as fillers and cement are mixed, the tensile elongation is reduced. When the elongation is less than 30%, the crack followability is remarkably deteriorated. A preferable tensile elongation is 50% or more, and more preferably 100% or more.

As a base | substrate (D) used for this invention, what was comprised by the cement concrete, asphalt concrete, ALC board, PC board, FRP, a plastics, a wooden thing, a metal, etc. individually or in combination is mentioned, for example. The shape may be any shape, and may be any surface such as a spherical surface, a curved surface, an extended surface, a flat surface, and a slope as long as the surface of the structure. Usually, it is a plane or a slope of cement concrete or asphalt concrete.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. Further, “parts” and “%” in the text are based on weight unless otherwise specified.
Synthesis Example 1 (Synthesis of methacrylic resin)
To a 5 L three-necked flask equipped with a thermometer, stirrer and cooler, diethylene glycol (D
EG) 3 mol, triethylene glycol (TEG) 7 mol, orthophthalic acid 10 mol, and toluhydroquinone 50 ppm were heat-condensed at 200 to 220 ° C, and cooled to 130 ° C when the acid value reached 27. Next, 2 mol of glycidyl methacrylate was charged and reacted at 130 ° C. for 4 hours to obtain polyester methacrylate. This was dissolved in methyl (meth) acrylate to obtain a methacrylic resin (hereinafter referred to as MMA-1) having a nonvolatile content of 65%.

Synthesis Example 2 (Synthesis of unsaturated polyester resin)
Heat dehydration condensation of 2.0 moles of cis-3-methyl-4-cyclohexene-cis-1,2-dicarboxylic acid, 2.5 moles of fumaric acid, and 5.25 moles of diethylene glycol by a conventional method In this way, an unsaturated polyester having an acid value of 18 was obtained. This was dissolved in methyl (meth) acrylate to obtain a liquid resin (1) (hereinafter referred to as UPE-1) having a nonvolatile content of 65%.

Synthesis example 3
To a 5 L three-necked flask equipped with a thermometer, stirrer and cooler, diethylene glycol (D
EG) 3.5 mol, triethylene glycol (TEG) 6.5 mol, phthalic anhydride 8.5 mol, and dibutyltin oxide 1000 ppm were charged, and the reaction was continued at 215 ° C. for 12 hours under a nitrogen stream. When it became below, it cooled to 150 degreeC, 1.5 mol of maleic anhydride was prepared, and it heated up to 205 degreeC. The reaction is continued for 16 hours at the same temperature. Sampling is performed with a 66.6% styrene solution, and the sample is cooled with an acid value of 10 to 20 and a Gadner viscosity of M to O.
30 ppm of toluhydroquinone and 10 ppm of copper naphthenate were added and diluted with styrene to obtain a liquid resin (2) (hereinafter referred to as UPE-2) having a nonvolatile content of 66%.

Resin for comparison (1)
Polylite FR-275M (general purpose FRP waterproof unsaturated polyester resin: tensile elongation 81%, tensile elastic modulus 400 MPa) manufactured by Dainippon Ink & Chemicals, Inc. was used.
Resin for comparison (2)
Polylite FR-250M (general purpose FRP waterproof unsaturated polyester resin: tensile elongation 48%, tensile elastic modulus 1230 MPa) manufactured by Dainippon Ink & Chemicals, Inc. was used.

Example 1
MMA-1 and UPE-1 are blended at a ratio of 85 parts / 15 parts, and 0.2 parts of curing accelerator dimethyl paratoluidine and 50% benzoyl peroxide (hereinafter referred to as BPO) paste for 100 parts of resin. Was added and cured at room temperature for 1 day, followed by post-curing at 80 ° C. for 6 hours.

Example 2
Curing accelerator 6% Cobalt Naphthenate 0.4 part and 55% for 100 parts of UPE-2
1.0 part of methyl ethyl ketone peroxide (hereinafter referred to as MEKPO) was added, cured at room temperature for 1 day, and then post-cured at 80 ° C. for 6 hours.
Comparative Examples 1 and 2
To 100 parts of resin, 1.0 part of 55% MEKPO was added and cured at room temperature for 1 day, followed by post-curing at 80 ° C. for 6 hours.
<Tensile test conditions>
The tensile test was performed by the method of JISK7113, and the test body shape was No. 1 dumbbell defined in the test method, and the thickness was about 3 mm. The test temperature was 23 ° C.
<Measurement of average linear expansion coefficient>
A cured product obtained in the same manner as the above-described specimen curing conditions was used as a specimen. The measurement was carried out using a thermal mechanical analysis method (TMA method) using EXSTAR-6000 manufactured by Seiko Instruments Inc.

<Calculation of stress generated by thermal expansion and contraction>
From the linear expansion coefficient and elastic modulus of the cured resin at around 23 ° C., the thermal stress generated when a temperature change of 20 ° C. was calculated. (See the formula below)
Thermal stress (MPa) = (tensile modulus) × (average linear expansion coefficient) × temperature change The test results are summarized in Table 1.
<Evaluation of adhesion between (A) layer and (C) layer>
Specimen specifications:
(D) Base JIS concrete flat plate (t = 60mm)
(C) Polymer composition layer Dick urethane N, manufactured by Dainippon Ink & Chemicals, Inc.) was applied and cured.
The coating thickness at this time was 2 mm. The above product is a polymer composition that conforms to urethane rubber specified in JIS A6021, and has a tensile elongation of 500% specified in JIS K6251.
(B) Adhesive layer Praiadec T-150-35 (one-part moisture-curing urethane primer, manufactured by Dainippon Ink & Chemicals, Inc.) was used. The coating amount at this time is 0.15 kg /
It was m ^2.
(A) Coating layer Each resin was impregnated into a glass mat # 450 of FRP waterproofing material industry association specification and cured to form a fiber reinforced resin layer. The resin / glass weight ratio at this time was 75/25 wt%.
The primer between D / C layers was 0.15 kg / m ^{2 of} Priadec T-150-35 as in (C).

<Adhesion evaluation method>
Procedure 1) (D) Apply the (C) layer on the substrate, and apply the (B) layer after curing for 24 hours.
Procedure 2) After applying the layer (B), leave it outdoors for 24 hours, and then apply the layer (A).
Procedure 3) Specimen completed in steps 1) and 2) is 23 ° C. × 1 week → 70 ° C. × 1
Week → 5 ° C x 1 week, 1 cycle for the cycle test and 2 cycles.
Procedure 4) After the end of the cold heat test, a skin was inserted between the layers (A) / (C) to confirm the presence or absence of peeling.
The test results are summarized in (Table-2).

＊；大日本インキ化学工業（株）製の一液湿気硬化型ウレタンプライマー
＊＊；大日本インキ化学工業（株）製の２液型ウレタン防水材。ＪＩＳＡ６０２１に規定するウレタンゴム系。

* One-part moisture-curing urethane primer manufactured by Dainippon Ink & Chemicals, Inc. **; Two-part urethane waterproofing material manufactured by Dainippon Ink & Chemicals, Inc. Urethane rubber system specified in JIS A6021.

Claims (4)

From the top (A) Coating layer in which a thermosetting resin having a tensile elongation of 90% or more at 23 ° C. and a tensile elastic modulus of 500 MPa or less is fiber reinforced (B) Adhesion for fiber reinforced thermosetting resin layer Agent layer (C) A composite coating structure having a polymer composition layer (D) substrate having a tensile elongation of 30% or more as defined in JISK6251. The composite covering structure according to claim 1, wherein the thermosetting resin of the layer (A) is at least one resin selected from the group consisting of unsaturated polyester resins, methacrylic resins, and vinyl ester resins. The composite covering structure according to claim 1 or 2, wherein the adhesive of the layer (B) is a moisture-curable urethane-based adhesive. The composite covering structure according to claim 1, wherein the polymer composition of the layer (C) contains a urethane rubber system defined in JIS A6021.