JP2009179989A - Floor structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a floor structure of a storehouse, a parking lot, etc., which is excellent in stationary steering resistance and weighting deformation resistance. <P>SOLUTION: This floor structure comprises a surface layer (A), a fiber-reinforced thermosetting resin-hardened material layer (B), a hardened material layer (C), and a substrate (D). The hardened material layer (C) includes an unsaturated resin composition (c1) which contains a vinylester resin (C-1), an air-dryable vinylester resin (C-2) and a polymerizable unsaturated monomer (C-3) and in which a tensile elongation percentage based on JIS K 6301 in the case of the composition (c1) as a hardened material is 30% or more, and silica sand (c2). In the volume of the hardened material layer (C), the volume of the silica sand (c2) is in the range of 25-80 vol.%. The hardened material layer (C) has a loading deformation of 0.3 mm or less. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a floor structure. More specifically, the present invention relates to a floor structure such as a warehouse or a parking lot that has excellent resistance to stationary and load-resistant deformation.

  The floor structure of civil engineering buildings, parking lots, etc. is the surface pavement layer (A), fiber reinforced thermosetting resin layer (B), adhesive layer for fiber reinforced thermosetting resin layer (C), JISK6301 Polymer composition layer (D) having a tensile elongation of 30% or more (specifically, urethane rubber types 1 and 2 which are waterproof coating materials for roofs according to JIS A6021, acrylic rubber type, chloroprene rubber type, An acrylic resin-based or rubber asphalt-based coating material) and a substrate (E) are known. (Patent Document 1)

  However, such a floor structure has a problem that if the steering wheel is turned before the forklift or the large automobile moves, the floor surface is deformed due to the load of the vehicle or the floor surface is cracked.

JP 05-33309 A

  An object of the present invention is a floor structure that does not cause deformation of the floor surface or cracking of the floor surface even if the handle is cut before the forklift or large vehicle moves, It is in a floor structure such as a civil engineering building and a parking lot that is excellent in stability and load-resistant deformation.

As a result of earnest research, the inventors of the present invention have completed the present invention as to how the floor structure can be achieved by achieving the floor structure.
That is, the present invention comprises (A) a surface layer from above,
(B) a fiber reinforced thermosetting resin cured product layer,
(C) an unsaturated resin composition (c1) comprising a vinyl ester resin (C-1), an air-drying vinyl ester resin (C-2) and a polymerizable unsaturated monomer (C-3), A cured product layer comprising an unsaturated resin composition (c1) having a tensile elongation of 30% or more in JISK6301 and a silica sand (c2) when the composition is a cured product,
(D) a floor structure comprising a substrate,
A floor structure characterized in that, of the volume of the cured product layer (C), silica sand (c2) is 25 to 80% by volume, and the cured product layer (C) has a deformation amount under load of 0.3 mm or less. It is to provide.

  In the present invention, a specific hardened material layer (C) is provided between the substrate (D) and the hardened material layer (B), so that a forklift or a large vehicle is turned before the handle is turned or a corner portion is run. However, the floor structure is not deformed by the load, or the floor surface is not cracked, that is, civil engineering buildings and parking lots, etc., which are excellent in upholstery resistance and load-resistant deformation resistance. A floor structure can be obtained. Moreover, since hardened | cured material layer (C) is unsaturated resin, a fiber reinforced thermosetting resin hardened | cured material layer (B) can be provided without interposing an adhesive bond layer.

  The basic (D) used in the present invention is composed of, for example, cement concrete, asphalt concrete, JIS5403 (asbestos slate), ALC board, PC board, FRP, plastic, wood, metal or the like alone or in combination. The shape may be any shape, and may be a spherical surface, a curved surface, an extended surface, a flat surface, a slope, or the like as long as the surface of the structure. Usually, it is a plane or a slope of cement concrete or asphalt concrete. A solid substrate such as concrete or metal is preferably subjected to a known base treatment and primer treatment.

  The cured product layer (C) used in the present invention is an unsaturated resin containing a vinyl ester resin (C-1), an air-drying vinyl ester resin (C-2), and a polymerizable unsaturated monomer (C-3). An unsaturated resin composition (c1) and silica sand (c2) having a tensile elongation of 30% or more according to JISK6301 when the composition is cured with a curing agent. In the volume of the cured product layer (C), the silica sand (c2) is 25 to 80% by volume, and the cured product layer (C) has a deformation amount of 0.3 mm or less under load. The volume% occupied by the silica sand (c2) in the volume of the cured product layer (C2) is 25 to 80% by volume. However, if it is out of this range, the amount of load deformation increases and the stationary resistance deteriorates. Preferably it is 35-70 volume%. The thickness of the cured product layer (C) is preferably 1 to 10 mm. In the present invention, the tensile elongation rate according to JISK6301 when the unsaturated resin composition (c1) is a cured product is 30% or more, preferably 100 to 260%.

The amount of load deformation refers to applying and curing an unsaturated resin composition to a substrate (cement concrete board, asphalt board) at two levels of 1.7 mm and 3.4 mm in thickness (described in the curing method) and curing at room temperature for 1 week. A tester penetration tester using a spring type (manufactured by Maruto Seisakusho Co., Ltd., used in the test method specified in JIS A 6204) is used, and a load of 10 kgf (self-weight) is applied to a needle having a diameter of 4 mm. including) applying a load 80 kgf / cm ² by applying a, the depth of the sunken needles and the load deformation amount.

  Examples of the vinyl ester resin (C-1) include unsaturated polyester (meth) acrylate resins, epoxy (meth) acrylate resins, urethane (meth) acrylate resins, and mixtures thereof.

  The unsaturated polyester (meth) acrylate resin is obtained from a saturated polyester obtained by a condensation reaction of a saturated dibasic acid and a polyhydric alcohol and a (meth) acrylate compound, and an α, β-unsaturated dibasic acid. There are those obtained from an unsaturated polyester obtained by condensation of a dibasic acid containing polyhydric alcohol and a (meth) acrylic compound.

  Examples of the saturated dibasic acid include phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, hexahydro Terephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3 -Naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, 4,4'-biphenyldicarboxylic acid, or dialkyl esters thereof.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,3- Examples include butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, 1,6-hexanediol, and the like.

  Examples of the unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride and the like.

  Examples of the (meth) acrylic compound include unsaturated glycidyl compounds, various unsaturated monobasic acids such as acrylic acid or methacrylic acid, and glycidyl esters thereof. Of these, glycidyl (meth) acrylate is preferred.

  The epoxy (meth) acrylate resin is obtained by reacting an epoxy resin with a carboxylic acid having a (meth) acrylol group, for example, a bisphenol type epoxy resin and a carboxylic acid having a (meth) acrylol group; And a reaction of a novolac type epoxy resin with a carboxylic acid having a (meth) acrylolyl group.

  Examples of the bisphenol type epoxy resin include a glycidyl ether type epoxy resin having substantially two or more epoxy groups in one molecule obtained by reaction of epichlorohydrin and bisphenol A or bisphenol F, methyl epichlorohydrin and bisphenol A, for example. Or the dimethyl glycidyl ether type epoxy resin obtained by reaction with bisphenol F, the epoxy resin obtained from the alkylene oxide adduct of bisphenol A, and epichlorohydrin or methyl epichlorohydrin, etc. are mentioned.

  Examples of the novolac type epoxy resin include an epoxy resin obtained by a reaction of a novolac type phenol resin or a novolac type cresol resin with epichlorohydrin or methyl epichlorohydrin.

  Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethyl malate, monobutene malate, sorbic acid, mono (2-ethylhexyl) malate, and the like. Alternatively, two or more kinds are used in combination.

  The urethane (meth) acrylate resin of the present invention is also called a vinyl urethane resin and is an oligomer of urethane (meth) acrylate using a polyol, an isocyanate, and a hydroxyl group-containing (meth) acrylate as raw materials.

  Such a urethane (meth) acrylate resin can be obtained by reacting a polyol and an isocyanate to obtain a terminal isocyanate group-containing prepolymer, and then reacting this with a hydroxyl group-containing (meth) acrylate.

  Examples of the polyol include polyether polyol and polyester polyol. Examples of such polyether polyols include polyoxypropylene diol, polytetramethylene glycol ether, and polyoxyethylene diol. Polyester polyols include dibasic acids or their anhydrides and polyhydric alcohols. A condensate is mentioned.

  Examples of such dibasic acids or acid anhydrides thereof include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, etc., and these may be used alone or in combination of two or more. It is done.

  Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, Examples include ethylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, and the like. These may be used alone or in combination of two or more.

  Next, examples of the isocyanate include 2,4-tolylene diisocyanate and its isomer or a mixture of isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexylmethane diisocyanate, and tolidine diisocyanate. And polyisocyanates such as naphthalene diisocyanate and triphenylmethane triisocyanate. Of these polyisocyanates, diisocyanates are preferred. These can be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing (meth) acrylates described above include hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate, and these are used alone or in combination of two or more.

  An air-drying vinyl ester resin (C-2) is used in combination with the unsaturated resin composition (c1) as a resin component. In this case, the amount used in combination is preferably 50% by weight or less. The non-volatile content (resin solid content) is preferably 50 to 80% by weight. If it deviates from this, the effect is not sufficient.

The air-drying vinyl ester resin (C-2) is a polymer obtained by introducing an air-drying component into the vinyl ester resin (C-1). Examples of the air-drying component include the following known components.
(1) A compound containing an allyl ether group represented by -0-CH ₂ -CH = CH ₂ is used in combination with the glycol component.
(2) A compound containing a cycloaliphatic unsaturated polybasic acid and a derivative thereof is used in combination with the acid component.
(3) A compound containing dicyclopentadiene is used in combination.
(4) A drying oil and an epoxy reactive diluent are used in combination.

  The mixing ratio of vinyl ester resin (C-1) and air-drying vinyl ester resin (C-2) is (C-1) :( C-2) ) = 99: 1 to 50:50 (parts by weight) is preferable. When the component (C-2) is more than 50, the cured resin has poor properties such as tensile strength, tear strength, water resistance, and moist heat resistance.

  The polymerizable unsaturated monomer (C-3) is an acrylic unsaturated monomer such as an acrylic ester or a methacrylic ester as a main component, and an acrylic unsaturated monomer that can be cross-linked with a resin. Or an acrylic unsaturated oligomer etc. are mentioned. The styrene monomer used in the unsaturated polyester resin should not be used because of odor. However, it can be used in combination so long as the effects of the present invention are not impaired. The amount of the styrene monomer used is preferably 30 parts by weight or less with respect to 100 parts by weight of the solid content of the resin (c1).

Silica sand (c2) is mainly composed of quartz grains and is generated by weathering of granite, etc., and is a siliceous material that is used as a raw material for silica (glass, ceramics, cement, brick) There is also artificial quartz sand that is crushed white rock, soft silica, furnace quartz, etc., regardless of whether it is natural or artificial in the present invention. In an integrated curve under the sieve obtained from the result of sieving 200 g of the silica sand continuously by applying vibration for 10 minutes using a known classifier such as an electromagnetic sieve shaker manufactured by Marui Co., Ltd. [High Sieve]. Silica sand whose particle size corresponding to% is 0.2 to 2.0 mm is preferred.
Silica sand distributed according to particle size range can be used alone or in a plurality of silica sands having different particle size ranges. When the particle size of silica sand is large, the composition of the hardened material layer (C) tends to improve the paint workability, and the aggregate blending ratio can be increased. Sedimentation of the material is likely to occur. Conversely, if the particle size is small, material separation (aggregation of aggregates) is less likely to occur, but the coating workability of blending the cured product layer (C) decreases. A combination of a plurality of silica sands having different particle size ranges is more preferable in order to achieve both of these conflicting tendencies.

  Such silica sand is preferably used in an absolutely dry state. When the water content increases, the tendency of inhibiting the curing of the unsaturated resin composition is exhibited.

  The resin composition preferably contains a curing agent in order to accelerate curing, and examples of the curing agent include organic peroxides. Specific examples of organic peroxides include diacyl peroxides, peroxyesters, hydroperoxides, dialkyl peroxides, ketone peroxides, peroxyketals, alkyl peresters, and carbonates. Can be mentioned. Furthermore, known curing agents such as a photocuring agent, an ultraviolet curing agent, and a thermosetting agent can be used alone or in combination.

  The addition amount of the curing agent is preferably 100 parts by weight of the total amount of the vinyl ester resin (C-1), the air-drying vinyl ester resin (C-2) and the polymerizable unsaturated monomer (C-3). And 0.1 to 6 parts by weight. You may use the said hardening | curing agent in combination of 2 or more types.

  The unsaturated resin composition (c1) preferably contains a curing accelerator, and examples of the curing accelerator include metal soaps such as cobalt naphthenate, cobalt octylate, and zinc octylate. Examples of chelate compounds include vanadium acetyl acetate and cobalt acetyl acetate. Examples of amines include known ones such as aniline and N, N-dimethylaniline.

  The addition amount of the curing accelerator is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the resin solid content. In the present invention, an amine accelerator is preferred. The curing accelerator may be added to the resin composition in advance or may be added at the time of use.

  It is preferable to add a polymerization inhibitor to the unsaturated resin composition (c1). Examples of the polymerization inhibitor include trihydrobenzene, hydroquinone, 1,4-naphthoquinone, parabenzoquinone, toluhydroquinone, hydroquinone monomethyl ether. , P-tert-butylcatechol, 2,6-tert-butyl-4-methylphenol, and the like. The amount used is preferably 10 to 1000 ppm in the composition.

  It is preferable to add a wax to the unsaturated resin composition (c1) in order to improve the air curability of the resin surface. As the wax, paraffin wax and / or polar wax can be used alone or in combination. This polar wax has both a polar group and a nonpolar group in its structure. Specifically, , Emanon 3199, 3299 (manufactured by Kao Corporation), Riquemar S-71-D, S-200 (manufactured by Riken Vitamin Co., Ltd.), NPS-8070, NPS-9125, OX-WEISSEN-8 (Nihon Seiwa ( Co., Ltd.) and Diacarna PA-30 (Mitsubishi Chemical).

  The amount of the wax added is 100 parts by weight based on the total amount of the vinyl ester resin (C-1), the air-drying vinyl ester resin (C-2) and the polymerizable unsaturated monomer (C-3). 0.1 to 5 parts by weight, preferably 0.2 to 2.0 parts by weight are used.

  The fiber reinforced thermosetting resin cured layer (B) is an unsaturated resin composition comprising the vinyl ester resin (C-1) and a polymerizable unsaturated monomer (C-3), or It is formed by impregnating a mat or sheet-like glass fiber reinforcing material with an unsaturated resin composition comprising a saturated polyester and a polymerizable unsaturated monomer and curing it. The thickness is preferably 1 to 3 mm.

  The surface layer (A) is formed by applying an acrylic resin such as an unsaturated resin type room temperature curable paint, a room temperature curable paint, or a room temperature dry paint, or an acrylic silicon paint. The thickness is preferably 0.1 to 0.5 mm.

The floor structure of the present invention can be obtained by applying to a base (D) of a civil engineering building. As the method, a primer material is applied to the base in an application amount of 0.02 to 0.5 kg / m ^2. Preferably, it is 0.05 to 0.25 kg / m ² . As a coating method, it is preferable that the coating is uniformly applied to the civil engineering building base with a brush, a roller, or the like. The base is an existing resin-coated floor, concrete, or the like, and preferably cement concrete. The base may constitute a civil engineering building such as a wall or a pillar other than the floor.

In the floor structure of the present invention, the unsaturated resin composition (c1) and the silica sand (c2) are mixed at the construction site, and preferably applied to the substrate at 1 to 15 kg / m ² rake or the like via a primer layer. Then, a cured product layer (C) is provided, and then a glass fiber reinforcing material is laid thereon, and the unsaturated resin composition is applied and impregnated and cured to form a fiber reinforced thermosetting resin cured product layer (B). To do. Furthermore, it is obtained by constructing the surface layer (A) thereon.

  Examples are shown below. In the text, “parts”, “%” and the like mean “parts by mass” and “% by mass” unless otherwise specified.

(Load deformation)
The load deformation amount is measured by applying a mixture of the composition (c1) and silica sand (c2) to the substrate (D) (cement concrete board, asphalt board) at two levels of thickness 1.7 mm and 3.4 mm (in the examples) Using a test plate that has been cured for 1 week at room temperature, using a spring-type Procter penetration tester (manufactured by Maruto Manufacturing Co., Ltd., JIS A 6204) Is applied using a needle having a diameter of 4 mm and a load of 80 kgf / cm ² is applied by applying a load of 10 kgf (including its own weight), and the depth of the submerged needle is taken as the amount of deformation. Asked.

(Stationary test)
In the stationary test, the substrate (D) (cement concrete board, asphalt board) was coated with a primer, a cured product layer (C), and a fiber reinforced thermosetting resin cured product layer (B). The results are shown in which a structure having 28 parts by mass was mounted at 50 revolutions per minute while applying a load of 80 kgf / cm ² from above the structure with a urethane rubber solid tire.

Synthesis Example 1 <Preparation of Primer>
In a four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser, 300 parts by mass of Millionate MR-200 (manufactured by Nippon Polyurethane Co., Ltd .: Crude MDI), polypropylene glycol (molecular weight 700, hydroxyl group) Equivalent 350) 210 parts by mass, dried toluene 474 parts by mass, and dried ethyl acetate 474 parts by mass were reacted at 80 ° C. for 5 hours to obtain a moisture curable urethane primer solution (p-1). The properties of the solution were appearance: brown liquid, free NCO%: 5.2 (per solid content: 14.8), solid content: 35%.

Synthesis Example 2 <Unsaturated Resin Composition (c1)>
In a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 283 parts by mass of Mitsui Polyoldiol 700 (manufactured by Mitsui Chemicals) and 144 of TDI (tolylene diisocyanate) A mass part was charged and maintained at 80 ° C. in a nitrogen atmosphere, and a theoretical NCO equivalent 516 was confirmed after reaction for 5 hours. The mixture was cooled to 30 ° C., charged with 109 parts by mass of 2-hydroxyethyl methacrylate, reacted at 80 ° C. for 4 hours, and when NCO% became 0.1% by mass or less, 358 parts by mass of methyl methacrylate, 0. 08 parts by mass, 0.026 parts by mass of tertiary butylcatechol, 0.1 part by mass of dimethylaniline, 0.4 parts by mass of 6% cobalt naphthenate were added, and a resin composition p-2 having a nonvolatile content of 60.0% was added. Obtained.

Synthesis Example 3 <Unsaturated Resin Composition (c1)>
In a 2-liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser, 208 parts by mass of neopentyl glycol, 270 parts by mass of 2-methyl-1,3-propanediol, adipine 292 parts by weight of acid, 308 parts by weight of hexahydrophthalic anhydride, 196 parts by weight of maleic anhydride and 0.255 parts by weight of monobutyltin oxide were heated to 205 ° C. in a nitrogen atmosphere, reacted for 4 hours, and 70% methacrylic. When the acid methyl solution reached an acid value of 60.8, it was cooled to 110 ° C. To this, 0.178 parts by mass of tolhydroquinone, 0.295 parts by mass of 2-methylimidazole, and 273 parts by mass of glycidyl methacrylate were reacted at 110 ° C. for 8 hours, and then 871 parts by mass of methyl methacrylate and 100 parts by mass of butyl acrylate. Part, 0.1 part by weight of tolhydroquinone, 0.1 part by weight of dimethylaniline, 0.4 part by weight of 6% cobalt naphthenate, and a resin composition p- having a nonvolatile content of 60.0% and an acid value of 1.2. 3 was obtained.

Synthesis Example 4 <Unsaturated Resin Composition (c1)>
Alcolysis was obtained by reacting 1.33 mol of glycerin and 0.67 mol of linseed oil at 180 to 200 ° C. for 4 hours. Next, 4 mol of diethylene glycol, 4 mol of dipropylene glycol, 5.0 mol of fumaric acid, 5.0 mol of phthalic anhydride, 0.1 part by mass of toluhydroquinone, 0.1 part by mass of dimethylaniline, 0% of 6% cobalt naphthenate The resin composition p-4 having an acid value of 25 was obtained by subjecting 4 parts by mass to heat dehydration condensation under known conditions.

Synthesis Example 5 <Unsaturated resin composition (c1)>
A four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser was charged with 332 parts of methyltetrahydrophthalic anhydride, and Neoallyl P-30 (pentaerythritol triallyl ether, manufactured by Daiso Corporation) 512 The reaction was carried out at 150 ° C. for 3 hours while adding part by mass and suppressing heat generation. When the acid value reached 67, which was almost the same as the theoretical value, the mixture was cooled to 120 ° C., 143 parts by mass of glycidyl methacrylate was added, and the reaction was carried out for 5 hours in an atmosphere of air / nitrogen = 1/1. When the acid value became 3 or less, 0.067 parts by mass of hydroquinone, 0.033 parts by mass of tertiary butylcatechol, 658 parts by mass of methyl methacrylate, 0.1 parts by mass of dimethylaniline, 0% of 6% cobalt naphthenate .5 parts by mass was added to obtain a resin composition p-5.

Synthesis Example 6 <Urethane resin for comparison>
8.9 parts by mass of polyoxypropylene triol (average molecular weight; 3000), 80.0 parts by mass of polyoxypropylene diol (average molecular weight; 3000), and tolylene diisocyanate (2,4-isomer 80% by mass) Of p-6-1, which is an isocyanate group-terminated polyurethane prepolymer having an NCO group content of 2.7% by mass, was reacted with 11.1 parts by mass of (NCO / OH molar ratio = 2.05).
In addition, 8.2 parts by mass of crude MBOCA (methylenebisorthoaniline dinuclear content 60.13% by mass), 28.5 parts by mass of dioctyl phthalate, 60 parts by mass of calcium carbonate, and pigment paste 3 parts by mass and 0.3 part by mass of octylic acid (lead content: 24% by mass) were added and mixed to obtain a curing agent composition p-6-2.

Synthesis Example 7 <Fiber reinforced thermosetting resin (B)>
1037 parts of orthophthalic acid, 294 parts by weight of maleic anhydride, 318 parts by weight of diethylene glycol and 1050 parts by weight of triethylene glycol and 0.135 parts by weight of toluhydroquinone were heated and condensed at 200 to 220 ° C. An unsaturated polyester having a heavy bond titer of 838 was prepared. To 67 parts by mass of the obtained resin, 33 parts by mass of styrene, 0.4 part by mass of 6% cobalt naphthenate and 0.1 part by mass of DMA (dimethylaniline) were added, and the resin p-7 for lamination was added. Obtained.

(Formulation example)
Resin compositions p-2 to 5 obtained in Synthesis Examples 2 to 5 were mixed at a ratio shown in the following table to obtain c1-1 to c1-4.
And the ratio of the main ingredient / hardening agent was mixed as 1/1 (NCO / NH2 molar ratio = 1.05) by mass ratio, and composition p-6 was obtained.

[Example 1]
Primer P-1 is applied onto concrete at 150 g / m ² and dried, and (C) layer is c1-1 / Seto quartz sand No. 5 / Niper NS (benzoyl peroxide 40% suspension; manufactured by NOF Corporation) = 100/150/3 was applied and cured at a thickness of 3 mm.
The amount of deformation of the cured coating film was 0.25 mm at 80 kgf / cm ² .
On top of that, as a layer (B), p-7 / Permec N (55% methyl ethyl ketone peroxide solution; manufactured by Nippon Oil & Fats Co., Ltd.) = 100/1 and glass mat # 450, GC (glass content) = 28%. Was laminated and cured.
Further, (A) 300 g / m ² of “Diobar HTP-550 (vinyl ester resin; manufactured by Dainippon Ink & Chemicals, Inc.) / Niper NS = 100/3” (a-1) was applied as a surface layer.
After curing for 7 days, a stationary test was conducted using a urethane rubber solid tire with a load of 80 kgf / cm ² assuming a forklift, and no abnormality was confirmed even at 100 revolutions.

[Example 2]
(C) layer on asphalt concrete c1-2 / Tohoku quartz sand No.3 / Tohoku quartz sand No.5 / Tohoku quartz sand No.7 / Cadox CH-50L (benzoyl peroxide 50% powder; manufactured by Kayaku Akzo Corporation) = 100 / 100/100/100/2 was applied and cured at a thickness of 5 mm.
The deformation of the cured coating film was 0.01 mm at 80 kgf / cm ² .
On top of that, it was laminated and cured with p-7 / Permec N = 100/1 and glass mat # 450 so that GC (glass content) = 28%.
Further, (A) “Diobar HTP-550 / Nyper NS = 100/3” (a-1) (a-1) was applied at 300 g / m ² as a surface layer.
After curing for 7 days, a stationary test was conducted using a urethane rubber solid tire with a load of 80 kgf / cm ² assuming a forklift, and no abnormality was confirmed even at 100 revolutions.

[Example 3]
Apply and dry primer P-1 at 150 g / m ² on cement concrete, and apply c1-3 / Tohoku quartz sand No. 6 / Kadox CH-50L = 100/200/2 as a layer (C) with a thickness of 3 mm. And cured.
The deformation of the cured coating film was 0.02 mm at 80 kgf / cm ² .
On top of that, the layer (B) was laminated and cured with p-7 / Permec N = 100/1 and glass mat # 450 so that GC (glass content) = 28%.
Further, (A) “Diobar HTP-550 / Nyper NS = 100/3” (a-1) (a-1) was applied at 300 g / m ² as a surface layer.
After curing for 7 days, a stationary test was conducted using a urethane rubber solid tire with a load of 80 kgf / cm ² assuming a forklift, and no abnormality was confirmed even at 100 revolutions.

[Example 4]
Primer P-1 is applied and dried on cement concrete at 150 g / m ² , and as layer (C), c1-4 / Kashima-2 / Tohoku quartz sand-7 / Kadox CH-50L = 100/700/100/2 It was applied and cured with a thickness of 10 mm.
The deformation of the cured coating film was 0.01 mm at 80 kgf / cm ² .
On top of that, layer (B) was laminated and cured with p-7 / Permec N = 100/1 and glass mat # 450 so that GC (glass content) = 28%.
Further, (A) a solvent-type acrylic urethane coating was applied as a surface layer at 300 g / m ² .

After curing for 7 days, a stationary test was conducted using a urethane rubber solid tire with a load of 80 kgf / cm ² assuming a forklift, and peeling of the surface layer was observed, but fiber reinforced thermosetting resin was observed even at 100 revolutions. No abnormality was confirmed in the layer below the cured product layer (B).

[Comparative Example 1]
Apply and dry primer p1 at 150 g / m ² on concrete, and apply c1-1 / Tohoku silica sand No. 5 / Cadox CH-50L = 100/50/2 as a layer (C) to a thickness of 3 mm, Cured.
The deformation of the cured coating film was 0.41 mm at 80 kgf / cm ² .
On top of that, layer (B) was laminated and cured with p-7 / Permec N = 100/1 and glass mat # 450 so that GC (glass content) = 28%.
Further, (A) “Diobar HTP-550 / Nyper NS = 100/3” (a-1) (a-1) was applied at 300 g / m ² as a surface layer.
After curing for 7 days, a stationary test was conducted using a urethane rubber solid tire with a load of 80 kgf / cm ² assuming a forklift, and the FRP layer was peeled off at 50 revolutions.

[Comparative Example 2]
Primer p-1 was applied on concrete at 150 g / m ² and dried, and (1) urethane resin c1-5 was applied and cured to a thickness of 3 mm. The amount of deformation of the cured coating film was 1.35 mm at 80 kgf / cm ² .
On top of that, layer (B) was laminated and cured with p-7 / Permec N = 100/1 and glass mat # 450 so that GC (glass content) = 28%.
Further, (A) “Diobar HTP-550 / Nyper NS = 100/3” (a-1) (a-1) was applied at 300 g / m ² as a surface layer.
After curing for 7 days, a stationary test was conducted using urethane rubber solid tires with a load of 80kgf / cm ² assuming a forklift. At 50 revolutions, the FRP layer and waterproof material layer were peeled off, and the underlying concrete was exposed. It was.

[Comparative Example 3]
On the asphalt concrete, the layer (B) was laminated and cured with p-7 / Permec N = 100/1 and glass mat # 450 so that GC (glass content) = 28%.
After curing for 7 days, a stationary test was conducted using a urethane rubber solid tire with a load of 80 kgf / cm ² assuming a forklift, and an abnormality occurred at the time of 10 rotations. The asphalt at the interface was cut back and was in a paste state.

  In Comparative Example 1, the volume fraction of silica sand is off and the load deformation amount is also off, so that it is inferior in anti-stabilization property. In Comparative Example 2, the tensile elongation rate of urethane resin is too large and the load deformation amount is large. In addition, it was inferior in the upright resistance, and Comparative Example 3 was inferior in the upright resistance because the cured product layer (C) was not present.

Claims (4)

(A) surface layer from above,
(B) a fiber reinforced thermosetting resin cured product layer,
(C) an unsaturated resin composition (c1) comprising a vinyl ester resin (C-1), an air-drying vinyl ester resin (C-2) and a polymerizable unsaturated monomer (C-3), A cured product layer comprising an unsaturated resin composition (c1) having a tensile elongation of 30% or more in JISK6301 and a silica sand (c2) when the composition (c1) is a cured product,
(D) a floor structure comprising a substrate,
Silica sand (c2) is 25 to 80% by volume of the volume of the cured product layer (C), and the cured product layer (C) has a deformation amount under load of 0.3 mm or less. The floor according to claim 1, wherein the fiber reinforced thermosetting resin cured layer (B) is obtained by impregnating and curing a glass fiber reinforcing material with a resin composition comprising an unsaturated polyester and a polymerizable unsaturated monomer. Structure. The floor structure according to claim 1 or 2, wherein the silica sand (c2) has a particle diameter of 0.2 to 2 mm corresponding to 80% in a cumulative curve under a sieve shaker. The floor structure according to any one of claims 1 to 3, wherein a tensile elongation percentage of JISK6301 of the cured product of the unsaturated resin composition (c1) is 100 to 260%.