JP4261394B2 - Construction method of waterproof composite coating - Google Patents

Description

The present invention relates to a construction method for a waterproof composite covering. More specifically, the present invention relates to a construction method for a waterproof composite covering useful as a lining construction method for a plane portion such as a building space represented by a veranda, a balcony, a flat roof, a floor surface and the like.

The construction method of waterproof composite coating is a waterproof construction method with high strength, surface hardness, excellent drainage, durability, dimensional stability, etc., and is represented by a veranda, balcony, flat roof, floor surface, etc. It is attracting attention as a lining method for flat surfaces such as spaces. In such a waterproof construction method, usually, first, after forming a ground with a gradient using concrete or mortar structure to improve waterproof performance, a fiber reinforced resin as a waterproof layer on the ground plane This is done by forming a layer and further providing a finishing material layer on the upper layer for the purpose of improving weather resistance, water resistance, etc., and improving aesthetics such as smoothness. In particular, in linings of houses such as verandas, balconies, flat roofs, etc., there are many cases where rooms are provided downstairs, and in order to prevent water leakage, etc., a slope is provided on the floor surface so that rainwater can be easily discharged. . However, since the construction for providing the gradient and the construction for providing the waterproof layer on the inclined layer are performed by different contractors, the construction period has been long. In addition, with the spread of energy-saving houses with high airtightness and high heat insulation, such verandas are also required to have heat insulation properties.

By the way, there is a partial revision of the Building Standards Law etc. as a countermeasure against sick house for building materials, and there is a risk of causing sanitary problems due to divergence regarding the development of technical standards concerning hygienic measures against the divergence of chemical substances in living rooms Formaldehyde is mentioned as a chemical substance. For example, as regards the rate of divergence of interior finishing materials, a material that emits formaldehyde in an amount exceeding 0.12 milligrams per hour per square meter of surface area in the summer is a type 1 formaldehyde-emitting building material (not used for interior finishing) Therefore, there is a need for a technique that can reduce the amount of formaldehyde emitted from the standard value to meet the building standards in the field of interior finishing materials.

The following prior art is disclosed as a technique related to construction in the conventional construction field and the like.
That is, a fiber reinforced plastic (FRP) panel is disclosed in which a fiber reinforced plastic layer is formed and integrated on a ground material with a gradient (see, for example, Patent Document 1). This FRP panel allows a single builder to simultaneously create a groundwork with a gradient and to form an FRP layer on the top surface, thereby preventing various time losses, delays in construction due to weather, lack of skills, etc. It is possible to eliminate it. (A) a polymerizable unsaturated monomer, (b) a polymer that is soluble or dispersible in the component (a), (c) a radical polymerization initiator, (d) a transition metal soap, and (e) the ( d) Regarding a radical polymerization curable construction material composition containing a compound that forms a complex or chelate with a transition metal in the component, a composition containing an acrylated unsaturated polyester and dibutylamine is disclosed as an example. (For example, refer to Patent Document 2). This composition is intended to reinforce a concrete structure, and the compound (e) such as dibutylamine is used for the delay effect of the polymerization initiation reaction in the polymerization and curing system. However, in these FRP panels and compositions, the curing process of the resin composition is suppressed by lowering the emission amount of formaldehyde and the like so that it can sufficiently cope with a partial revision of the Building Standard Law and the like. In addition, the risk of causing sanitary problems in cured products is sufficiently suppressed, and there is room for further improvement in waterproofing.
JP-A-8-193409 International Publication No. 99/62977 Pamphlet

The present invention has been made in view of the above situation, and is excellent in waterproof performance such as drainage, weather resistance, and water resistance, heat insulation performance, aesthetics such as smoothness, and can be simply and efficiently lined. Further, it is an object of the present invention to provide a method for constructing a waterproof composite covering capable of sufficiently suppressing the risk of causing sanitary problems when the amount of formaldehyde emission is sufficiently reduced.

The present inventors have made various studies on the waterproof lining method, and as a result, a method for constructing a waterproof composite coating comprising at least a heat insulating layer, a base plate layer, a fiber reinforced resin layer, and a finishing material layer laminated in this order on a substrate. Then, paying attention to the fact that it is possible to obtain a waterproof composite covering capable of exhibiting a heat insulating effect in addition to being excellent in waterproof performance such as drainage, weather resistance, water resistance and smoothness, and further, a heat insulating layer If the slope is provided with a slope to improve waterproofness and the thermal insulation layer is inclined, the slope can be easily provided without complicated work compared to the case where the slope is provided on the base using a joist etc. It has been found that it is possible to carry out efficiently. In addition, according to such a construction method, since it is not necessary to provide a gradient at the time of construction, the construction period can be shortened, and since it is structurally simple, the advantage that the overall weight can be suppressed can be exhibited. And the fiber reinforced resin layer contains an unsaturated polyester having a specific double bond titer, a polymerizable monomer and an alicyclic amine, and has a specific tensile strength and tensile elongation rate. It is found that the waterproof performance of the fiber reinforced resin layer is further improved and the formaldehyde emission amount can be sufficiently reduced in the curing process and cured product of the resin composition by combining these layers. They found out that it would be a very useful construction method as a lining method for flat surfaces of architectural spaces, etc., and came up with the idea that the above problems could be solved brilliantly. In addition, in such a construction method, when fire prevention is necessary, forming the above-mentioned base plate layer using a non-combustible material such as calcium silicate provides a waterproof composite covering that can exhibit excellent fire prevention performance. It has been found that this is possible, and the present invention has been achieved.
In addition, the construction method of the composite covering for waterproofing according to the present invention is subject to the “Act on Partial Revision of the Building Standards Act Related to Sick House Measures” in the revised Building Standards Law that came into effect on July 1, 2003. The final products such as building materials in the building field and the like can sufficiently reduce the amount of formaldehyde emitted.

That is, the present invention is a method for constructing a waterproof composite covering obtained by laminating at least an inclined heat insulating layer, a base plate layer, a fiber reinforced resin layer, and a finishing material layer in this order on a substrate, the fiber reinforced resin layer Is composed of a room temperature curable resin composition containing an unsaturated polyester resin having a double bond titer of 300 to 1800 and an alicyclic amine, and the room temperature curable resin composition has a tensile strength in a cured product. Is a construction method of a waterproof composite covering having a tensile elongation of greater than 10% and a tensile elongation of greater than 10%.
The present invention is described in detail below.

The construction method of the waterproof composite covering according to the present invention is formed by laminating at least an inclined heat insulating layer, a base plate layer, a fiber reinforced resin layer, and a finishing material layer in this order on a substrate.
In the construction method, examples of the base part include building roofs, fences, open corridors, verandas, balconies, factory floors, etc., and the materials thereof are concrete, asphalt, asbestos slate, foamed concrete, plastic, wood, Metal etc. are mentioned.
When the base is concrete, asphalt, or asbestos slate, it can be applied without an incombustible layer, and the surface water content is preferably 5% or less.
When the base is made of wood, it is preferable to stack a base plate (base), joist (gradient batten), a sloped heat insulating layer, a base plate layer, a fiber reinforced resin layer, and a finishing material layer in this order. .

The inclined heat insulating layer in the above construction method is composed of a heat insulating material with a gradient, and using a heat insulating material formed on a flat plate, the thickness is continuously changed so that at least one surface has a constant gradient. It is preferable to use the same. In the present invention, by providing a heat insulating layer, it is possible to impart or improve heat insulating properties and moisture proof, can exhibit energy saving and indoor dew condensation prevention function, and further by providing a gradient in the heat insulating layer Since the waterproofing of the construction surface can be improved, it can be suitably used for a house veranda. Also, compared to the case where a slope is provided on the base using a joist or the like, the slope can be easily provided without requiring special skills, so that waterproof construction with good drainage can be performed more efficiently. It becomes possible.

Examples of the heat insulating material include hard and foamable resins such as urethane foam, vinyl chloride foam, acrylic foam, styrene-polyethylene graft mixed foam, phenol foam, polystyrene foam, carbonized cork, and foamed glass.
The gradient provided in such a heat insulating material preferably has an inclination angle (θ) of 1/100 or more when the horizontal direction is 0 °. In addition to using a commercially available material, the gradient can be provided by cutting the heat insulating material at a construction site or the like.
The inclined heat insulating layer is preferably formed by fixing to the base with a screw so as not to move, or fixing to the base with an adhesive or an adhesive.

Hereinafter, an example of a method for forming the inclined heat insulating layer will be described with reference to the drawings, but the present invention is not limited thereto.
As the heat insulating material with a gradient, one having an inclination angle (θ) as exemplified in FIGS. 2A to 2C can be used. For example, two or more types of heat insulating materials having different inclination angles and thicknesses can be used. It can also be used.
(1) First, as shown in FIG. 3 (e), after attaching a drain (drainage port) 6 to a construction surface such as a house veranda, the insulating material 7 with a slope for drainage groove is inclined toward the water from the drain position. Arrange in order.
(2) Then, as shown in FIG.3 (f), the flat field gradient heat insulating material 8 is arrange | positioned in order of a gradient.
(3) Next, as shown in FIG. 3 (g), the sloped heat insulating material 9 is appropriately adjusted so that a constant slope is continuously formed in accordance with the thickness of the arranged heat insulating material on the side opposite to the drain 6. Alternatively, a heat insulating material 10 or the like having no inclination angle as shown in FIG.
In addition, after providing an inclined heat insulation layer in this way, field board layers, such as a plywood, will be stuck on the whole surface.

Moreover, although an example of the fixing method of the heat insulating material which forms the said gradient heat insulation layer is further demonstrated using figures, this invention is not limited to these.
First, as shown in FIG. 4, after placing the heat insulating material 2 on the base body 1, the field board 3 serving as the field board layer is placed. A joint tape (not shown) with an adhesive such as an adhesive butyl non-woven tape is applied to the joint portion of the base plate to perform joint treatment. Next, the base plate and the heat insulating material are penetrated through the fixing plate 11 from above the base plate and fixed to the base body 1. It is desirable to apply a resin putty made of a polyester resin or the like to the head portion of the fixing metal to smooth the surface. In addition, the fiber reinforced resin layer 4 and the finishing material layer 5 are formed thereon.
The fixing bracket is not particularly limited as long as it is conventionally used in a machine fixing method, but holds down a wood screw, a tapping screw, a self-drilling screw, an anchor portion (nail portion) inserted into a base, a field plate, or the like. What consists of a disk part (or plate part) is used.
Examples of the material of the fixing metal include iron, stainless steel, galvanium, UNIQLO, and aluminum, but need not be literally “metal”, and may be a plastic product.

As a method for fixing the wood screw or the like to the base, for example, a pilot hole is drilled in advance, and an open leg plug (a plug set to increase the pulling strength from the base by opening the plug) is used. The integrated screw can be fixed by a method (screwing method) using an electric drill or the like. In addition, when fixing to ALC (lightweight cellular concrete) or the like having a weak base strength, it is preferable to fix the fixing bracket by injecting epoxy resin or the like into the pilot hole in order to increase the pulling strength.
Examples of the material of the open leg plug include plastics such as nylon, zinc alloy, lead / antimony alloy, and the like.
As a method of fixing the wood screw or the like to the base body, it may be a combined type in which the heat insulating material is fixed with an adhesive at the rising portion of the parapet or the like, and is mechanically fixed at the flat portion, particularly on the existing waterproof layer. When fixing a heat insulating material etc., workability | operativity can be improved further and it is suitable.

The field board layer in the construction method is composed of a field board, and can be formed using, for example, plywood.
When fire prevention is necessary, the above-mentioned base plate layer may be a non-combustible layer, and the form in which the above-mentioned base plate layer is a non-combustible layer is one of the preferred embodiments of the present invention. In addition, as a construction method in this case, it is as having mentioned above (or mentioned later) except having made the field board layer into the nonflammable layer.
The incombustible layer is composed of an incombustible material, and examples thereof include flat plates such as concrete, brick, glass, rock, metal, wood wool cement board, gypsum board, and calcium silicate board. Among them, it is preferable to use a calcium silicate plate that has been certified as non-combustible according to JIS A5430 (2001). In this invention, by providing such a nonflammable layer, a fireproof function can be provided and it will be used suitably for a wooden house etc.
The above-mentioned base plate layer and incombustible layer are preferably formed by fixing to the heat insulating layer or the base with screws so as not to move, or fixing to the heat insulating layer with an adhesive or a pressure sensitive adhesive. . In addition, it is preferable to chamfer the entrance corner and the exit corner.

In the construction method, next, a fiber reinforced resin (FRP) layer forming step is performed. When a fiber reinforced resin layer is constructed, a base plate layer or a non-combustible layer surface serving as a foundation thereof is used. It is preferable to apply a primer in an amount of 0.1 to 1 kg / m ² as necessary. As a primer, an epoxy resin, a polyurethane resin, an unsaturated polyester resin, a vinyl ester resin, an acrylic resin, a urethane acrylate resin, or the like is preferable. In addition, after the primer is cured, a soft resin may be applied in an amount of 0.1 to ² kg / m ^{2 in} order to improve followability with the base plate layer or the incombustible layer. As the soft resin, an unsaturated polyester resin, an epoxy resin, a polyurethane resin, a urethane acrylate resin, or the like is suitable, and the elongation percentage of the cured product is preferably 30 to 300%.
Furthermore, in order to improve the adhesion with the base, fillers such as silica sand and talc may be blended, and the amount used is 50 to 300 parts by weight with respect to 100 parts by weight of the soft resin. Is preferred.

The fiber reinforced resin layer is preferably formed by being cured in a state where the fibrous reinforcing material and the room temperature curable resin composition are combined, and the fibrous reinforcing material may be glass fiber, metal fiber, or the like. 1 type or 2 or more types such as ceramic fiber and carbon fiber can be used, and the shape is one or more types such as chopped strand mat, cloth (woven fabric), nonwoven fabric, three-dimensional fabric Can be used. The amount of the fibrous reinforcing material used is 8 to 80% by mass, preferably 10 to 60% by mass, assuming that the total material forming the fiber reinforced resin layer is 100% by mass. It is set appropriately according to the above.

In the fiber reinforced resin layer, it is appropriate to use an unsaturated polyester having a double bond titer of 300 to 1800, a polymerizable monomer and an alicyclic amine as the room temperature curable resin composition. It is. In addition, in this invention, the unsaturated polyester resin which consists of unsaturated polyester and a polymerizable monomer means what can be radically polymerized at normal temperature.
In the unsaturated polyester, if the double bond titer is less than 300, the followability to the movement of the base substrate in the waterproof composite coating may not be sufficient, and if it exceeds 1800, the fiber reinforcement There is a possibility that the resin layer may not have excellent load resistance, wear resistance, and the like. Preferably, it is 400-1600, More preferably, it is 500-1400.
The double bond titer is the number of grams of unsaturated polyester per mole of polymerizable double bond. For example, the following formula:
Double bond titer = obtained from {(acid component + glycol component) -condensed water} / mole number of unsaturated acid.

By the way, when the waterproof material is used for a veranda or an indoor floor, the fall of foreign matters is unavoidable, and the impact property against these is one of the required physical properties. By using an unsaturated polyester satisfying the above range for the fiber reinforced resin layer, it has a performance that can sufficiently withstand the fall of foreign matters. When a polymer having a double bond titer of less than 300 is used, crushing is confirmed by a falling ball impact.

In the room temperature curable resin composition, the alicyclic amine is used for the purpose of capturing formaldehyde, and for example, one or more of morpholine, piperidine, piperazine, pyrrolidine and the like are suitable. . In addition, an alicyclic amine may be previously mix | blended in a resin composition, and may be mix | blended just before making it harden | cure. In addition, the alicyclic amine used in the present invention includes an amine compound formed by reacting a pre-blended alicyclic amine in the skeleton or other compound in the resin composition.
As for the usage-amount of the said alicyclic amine, it is preferable that an upper limit is 3 weight part and a minimum is 0.01 weight part with respect to 100 weight part of unsaturated polyester resins. A more preferred upper limit is 1.5 parts by weight and a lower limit is 0.05 parts by weight. Moreover, a preferable range is 0.01-3 weight part, and a more preferable range is 0.05-1.5 weight part. By setting to such a range, it is possible to sufficiently exert the effect of the present invention that the formaldehyde emission amount is sufficiently reduced.

In the said room temperature curable resin composition, it becomes possible to fully suppress generation | occurrence | production of formaldehyde after a hardening process and hardening. The formaldehyde emission amount in the cured product of the resin composition is preferably 1.8 mg / L or less. More preferably, it is 0.35 mg / L or less, More preferably, it is 0.12 mg / L or less.

The room temperature curable resin composition also has a tensile strength in a cured product of the room temperature curable resin composition of greater than 10 MPa and a tensile elongation of greater than 10%. If the tensile strength is 10 MPa or less, the waterproofness, water resistance, followability to the substrate and the like of the formed fiber reinforced resin layer may not be sufficiently improved, and the tensile elongation is 10% or less. If so, the rigidity of the cured layer formed from the room temperature curable resin composition becomes too high, and there is a possibility that the followability to the expansion and contraction and vibration of the substrate such as a wooden material may not be sufficient.
As said tensile strength, it is more preferable that it is 15 MPa or more, More preferably, it is 20 MPa or more. Moreover, it is more preferable that it is 50 MPa or less, More preferably, it is 40 MPa or less.
As said tensile elongation rate, it is more preferable that it is 20% or more, More preferably, it is 30% or more. Moreover, it is more preferable that it is 200% or less, More preferably, it is 100% or less.
In addition, it is preferable to measure the tensile strength and tensile elongation rate in the hardened | cured material of a resin composition based on Japanese Industrial Standard (JISK7113 (1995)).

Examples of the method for forming the fiber reinforced resin layer include a method in which a room-temperature curable resin composition is applied, a fibrous reinforcing material is applied, and a room-temperature curable resin composition is applied and then cured; It is possible to form a fiber reinforced resin layer by a method of impregnating a fiber composition with a fiber reinforced material by hand layup or the like to form a coating material and curing the resin composition. In addition, it is preferable that such a fiber reinforced resin layer is lined with 0.5-5 kg / m < ² >.
As a method for applying the room temperature curable resin composition, for example, a coating method such as brush coating, roll brush coating, spray coating or the like can be used.
Moreover, as a method of curing the room temperature curable resin composition, for example, immediately before the construction, all the components including the curing agent are mixed to create a resin composition, or the resin composition is removed in advance by removing the curing agent. It can be cured by adjusting and mixing a curing agent just before construction. Moreover, it is preferable to carry out at normal temperature as hardening temperature on hardening conditions. More preferably, it is -10-60 degreeC, More preferably, it is 10-40 degreeC. The gelation time is preferably 1 to 180 minutes. More preferably, it is 5 to 60 minutes.

In the above construction method, the finishing material layer is then formed. Before the finishing material layer is formed, after the fiber reinforced resin layer is cured, the surface is cleaned with a disk sander or the like, and a glass mat or the like. It is preferable to keep the trace of the surface flat.
The finishing material layer is preferably composed of a resin composition containing one or more of paints such as fluorine, acrylic silicon and polyurethane, unsaturated polyester resins, acrylic resins and vinyl ester resins. In addition, if necessary, pigments can be added and colored for use. Among them, those that are curable at room temperature are preferably used, and the coating materials of these finishing materials, like the room temperature curable resin composition, have a formaldehyde emission amount of 1.8 mg / L or less in the cured product of the resin composition. Preferably there is. More preferably, it is 0.35 mg / L or less, More preferably, it is 0.12 mg / L or less.
As such a resin composition, the above-mentioned alicyclic amine may be included, and as an appropriate form, an unsaturated polyester resin composition containing an unsaturated polyester, a polymerizable monomer and an alicyclic amine. It is a form that is a thing.

The finishing material layer is preferably formed by applying 0.2 to 1 kg / m ^{2 of the} resin composition, and the raw material, the application method, and the curing method are described above in the fiber reinforced resin layer (or It is the same as that described later.
In addition, in the finishing material layer in this invention, you may give a color design and can perform granite finishing, for example. Further, the anti-slip property can be improved by increasing the surface roughness of the finishing material layer.

Examples of the particles (aggregate) to which the design properties are applied include crushed stone, gravel, pebbles, slag, and the like, and the particle size thereof is preferably in the range of, for example, about 0.1 to 3 mm, more preferably 0. The range is 5 to 1 mm.
As the particles (aggregates), No. 6 (150 to 600 μm) crushed stones, glass beads, and the like are preferably used to exhibit anti-slip properties.
The amount of the particles (aggregate) used is preferably, for example, an occupied area in the range of 1/3 to 1/10 of the construction surface. If it is less than 1/10 of the construction surface, sufficient design properties may not be obtained. If it exceeds 1/3, the average strength physical properties of the construction surface may not be sufficiently obtained. More preferably, it is the range of 1/5 to 1/7.

In the construction method of the waterproof composite covering of the present invention, after the fiber reinforced resin layer is formed, at least 3 days later, the finishing material layer is applied without performing a ground treatment for expressing adhesion. As a result, construction usually performed in the construction method of the waterproof composite covering from the formation of the fiber reinforced resin layer to the formation of the finishing material layer, for example, walls, pillars, interior materials, and other fixtures It is possible to install and move equipment and fixtures. As described above, the construction method of the waterproof composite covering for constructing the finishing material layer without performing the ground treatment for expressing the adhesion after at least 3 days after the formation of the fiber reinforced resin layer is suitable for the present invention. This is one of the forms.
In this construction method, “underlying treatment for expressing adhesiveness” means that the entire surface or a part of the surface of the fiber reinforced resin layer is sanded to such an extent that the surface condition changes and the adhesiveness is expressed. It means that a primer layer (adhesive layer) is provided on the entire surface or a part of the reinforced resin layer. In the present invention, the finishing material layer may be formed after one week or more has elapsed since the formation of the fiber reinforced resin layer.

In the present invention, in such a construction method, the waterproof composite cover is excellent in waterproof performance such as drainage, heat insulation, weather resistance, water resistance, etc. Although it will construct so that it may adhere to a fiber reinforced resin layer, in order to construct in that way, the room temperature curable resin composition which forms a fiber reinforced resin layer, and the resin composition which forms a finishing material layer It is preferable to appropriately adjust the blending of these. For example, it can be adjusted by blending a specific amount of paraffin wax or the like for improving the surface drying property into the room temperature curable resin composition forming the fiber reinforced resin layer and the resin composition forming the finishing material layer. Preferably, this makes it possible to carry out the construction usually accompanied by the construction method of the waterproof composite covering between the formation of the fiber reinforced resin layer and the formation of the finishing material layer. It is constructed so as to be sufficiently adhered to the fiber reinforced resin layer.

In the above construction method, a finishing material layer is formed at least 3 days after the formation of the fiber reinforced resin layer, and the finishing material layer is laminated on the fiber reinforced resin layer without performing a ground treatment for expressing adhesion. As the adhesiveness of the finishing material layer when forming the coating material, for example, a finishing material (resin composition constituting the finishing material layer) is applied 3 days after the formation of the fiber reinforced resin layer, and the finishing material is applied 24 hours later. When the finish material adhesion (gap spacing 2 mm, number of squares 25) is evaluated by a cross-cut method according to JIS K5400 (1990) 8.5.2, the adhesion evaluation score is 6 points or more. It is preferable. More preferably, the adhesion evaluation score when the finishing material is applied one week after the formation of the fiber reinforced resin is 6 points or more, and more preferably 8 points or more. The adhesion evaluation table shown in JIS K5400 (1990) is shown in Table 1.

According to the construction method of the waterproof composite coating of the present invention, the mechanical properties such as waterproofness, heat insulation, water resistance, followability to the substrate, load resistance, wear resistance, etc. are excellent, as well as chemical resistance, It is possible to obtain a waterproof composite coating that has additional performance such as long-term durability, and that can sufficiently reduce the amount of formaldehyde emitted after the curing process and after curing. The waterproof composite covering constructed by the above is also one aspect of the present invention.

Below, the room temperature curable resin composition which forms a fiber reinforced resin layer and the room temperature curable resin composition suitable as a resin composition which forms a finishing material layer are further demonstrated.
In these room temperature curable resin compositions, the unsaturated polyester resin includes an unsaturated polyester and a polymerizable monomer as described above, and is obtained by mixing stabilizers and various additives as necessary. be able to.
The unsaturated polyester can be obtained by a condensation reaction between a polybasic acid component and a glycol component and / or an epoxy compound component.
The polybasic acid component used in the unsaturated polyester has two or more substituents that can react with a hydroxyl group and / or an epoxy group contained in a glycol component and / or an epoxy compound component to form an ester bond. Any compound may be used, and an unsaturated polybasic acid is essential, and a part thereof may be replaced with a saturated polybasic acid.
Examples of the unsaturated polybasic acid include α, β-unsaturated polybasic acids such as maleic acid, fumaric acid, aconitic acid, and itaconic acid; β, γ-unsaturated polybasic acids such as dihydromuconic acid; One or more of acid anhydrides; halides of these acids; alkyl esters of these acids, and the like can be used.

Examples of the saturated polybasic acid include malonic acid, succinic acid, methyl succinic acid, 2,2-dimethyl succinic acid, 2,3-dimethyl succinic acid, hexyl succinic acid, glutaric acid, 2-methyl glutaric acid, 3- Aliphatic saturated polybasic acids such as methyl glutaric acid, 2,2-dimethyl glutaric acid, 3,3-dimethyl glutaric acid, 3,3-diethyl glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid Aromatic aromatic polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and pyromellitic acid; het acid, 1,2-hexahydrophthalic acid, 1,1-cyclobutanedicarboxylic acid, trans-1, Alicyclic saturated polybasic acids such as 4-cyclohexanedicarboxylic acid and dimer acid; anhydrides of these acids; halides of these acids; It can be used alone or in combination of two or more such alkyl ester.

Examples of the glycol component used in the unsaturated polyester include ethylene glycol, diethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, and 1,3-butanediol. 2,3-butanediol, dipropylene glycol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-1, 4-butanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanediol, 1,4-dimethylolcyclohexane, 2, 2-diethylpropane-1,3-diol, 3-methylpentane-1,4 Diol, 2,2-diethylbutane-1,3-diol, 4,5-nonanediol, triethylene glycol, hydrogenated bisphenol A, alkylene oxide adduct of bisphenol A, alkylene oxide adduct of hydrogenated bisphenol A, glycerin , Trimethylolpropane, pentaerythritol, dipentaerythritol and the like can be used alone or in combination.

Examples of the epoxy compound component used in the unsaturated polyester include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, 3,4-epoxy-1-butene, glycidyl acrylate, glycidyl methacrylate, and diglycidyl ether of bisphenol A. 1 type (s) or 2 or more types can be used.

A part of the raw material of the unsaturated polyester may be replaced with a compound having an unsaturated bond such as an allyl group shown below, and in this case, a so-called air-curable polyester can be obtained. Specifically, at least the whole amount or part of the above-mentioned normal polybasic acid component is replaced with an unsaturated polybasic acid having an unsaturated bond such as an allyl group shown below, or the above-mentioned normal glycol component and / or Alternatively, the entire amount or a part of the epoxy compound component may be replaced with a glycol component having an unsaturated bond such as an allyl group and / or an epoxy compound component shown below.

Examples of the unsaturated polybasic acid component having an unsaturated bond include tetrahydrophthalic anhydride, α-terpinene-maleic anhydride adduct, cyclopentadiene-maleic anhydride adduct (endomethylenetetrahydrophthalic acid), rosin, 1 type (s) or 2 or more types, such as ester gum, drying oil fatty acid, semi-drying oil, and a fatty acid, can be used.
Examples of the glycol component and / or epoxy compound component having an unsaturated bond include trimethylolpropane monoallyl ether, trimethylolpropane diallyl ether, trimethylolethane monoallyl ether, trimethylolethane diallyl ether, and pentaerythritol monoallyl ether. , Pentaerythritol diallyl ether, pentaerythritol triallyl ether, glycerol monoallyl ether, glycerol diallyl ether, allyl glycidyl ether and the like can be used.

The terminal hydroxyl group of the unsaturated polyester can also be used by reacting with a polyfunctional isocyanate. The polyfunctional isocyanate to be reacted is not particularly limited. For example, phenylene diisocyanate, 2,4- or 2,6-toluene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, Examples include diisocyanates such as forone diisocyanate; triisocyanates such as triphenylmethane triisocyanate and 1,3,6-hexamethylene triisocyanate. These can be used alone or in combination.
The polyfunctional isocyanate is used in an amount of 0.1 to 10% by mass, preferably 0.3 to 5% by mass, based on 100% by mass of the unsaturated polyester. What is necessary is just to perform the reaction method at the time of obtaining the unsaturated polyester formed by making the said unsaturated polyester and the said polyfunctional isocyanate react, and carrying out urethane modification according to a well-known method in the said industry. For example, in the presence of a polymerization inhibitor such as hydroquinone or oxygen and a urethanization catalyst such as a tin compound or tertiary amine, a radically polymerizable unsaturated monomer (polymerizable monomer) described below may be present as necessary. The unsaturated polyester and the polyfunctional isocyanate may be reacted at room temperature to 130 ° C.

In the unsaturated polyester resin, examples of the polymerizable monomer include styrene, vinyltoluene, paramethylstyrene, chlorostyrene, divinylbenzene, vinyl acetate; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meta ) Monofunctional alkyl (meth) acrylates such as acrylate and hexyl (meth) acrylate; cyclic in the molecule such as cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, isobornyl methacrylate, dicyclopentenyloxyethyl methacrylate, and phenoxyethyl methacrylate Monofunctional (meth) acrylate having structure; (poly) ethylene glycol di (meth) acrylate, neopentyl glycol dimethacrylate, (poly) propylene Polyfunctional (meth) acrylates such as polyglycol di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, trimethylolpropane tri (meth) acrylate, etc., and these may be used alone, Two or more kinds may be used in combination. Among these, it is preferable to use styrene.

In the polymerizable monomer, when styrene is used, it is preferably 50 to 100% by mass when the total amount of the polymerizable monomer is 100% by mass.
A preferred form of the polymerizable monomer is one having a viscosity at 25 ° C. of 100 mPa · s or less. When the viscosity exceeds 100 mPa · s, the viscosity of the room temperature curable resin composition increases, and the workability may not be sufficient.

In the unsaturated polyester resin, the mass ratio of the unsaturated polyester and the polymerizable monomer is preferably (20 to 80) / (80 to 20) of unsaturated polyester / polymerizable monomer. If the mass ratio of the polymerizable monomer exceeds 80% by mass, the resulting resin may not have sufficient chemical resistance and toughness. If it is less than 20% by mass, the cured product will have sufficient surface properties. In addition, the viscosity cannot be improved and the workability may not be excellent.
In the unsaturated polyester resin, a stable radical such as hydroquinone, catechol, t-butylcatechol, benzoquinone, cresol, t-butylhydroquinone, ferdazil, DPPH (diphenylpicrylhydrazyl) may be used as a stabilizer. it can.

In this way, an unsaturated polyester resin contained in the room temperature curable resin composition can be obtained, and among them, dicyclopentadiene (DCPD) unsaturated polyester resin and / or recovered polyethylene terephthalate (PET) is used. Unsaturated polyester resin may be used. Note that “using recovered PET” means that recovered PET was used as a raw material.

The dicyclopentadiene-based unsaturated polyester resin is obtained by dissolving an unsaturated polyester having a norbornene skeleton in the polymerizable monomer described above. The unsaturated polyester (I) having a norbornene skeleton (hereinafter also referred to as “unsaturated polyester (I)”) is a norbornene skeleton represented by the following general formula (1) at a part of the molecular terminal of the unsaturated polyester. Refers to those introduced.

The acid value and molecular weight of the unsaturated polyester (I) are not particularly limited, but generally the acid value is 40 or less, the number average molecular weight is 500 to 5000, and the weight average molecular weight is in the range of 1000 to 50000. It is preferable that the number average molecular weight is in the range of 600 to 2500 and the weight average molecular weight is in the range of 1500 to 15000 from the viewpoint of the balance between low viscosity and physical properties of the cured product. These molecular weight measurements can be easily obtained by using a general-purpose gel permeation chromatography (GPC) apparatus and measuring polystyrene having a known molecular weight as a standard substance and a differential refractometer as a detector.

The method for introducing the norbornene skeleton into the unsaturated polyester is not particularly limited. For example, a method of introducing dicyclopentadiene as a raw material is efficient and economical. Specifically, for example, it can be obtained by replacing a part of the polybasic acid component used in the unsaturated polyester with an unsaturated polybasic acid adduct of dicyclopentadiene. As the unsaturated polybasic acid adduct of dicyclopentadiene, an adduct obtained by adding the above-mentioned unsaturated polybasic acid to dicyclopentadiene, for example, a dicyclopentadiene maleic acid adduct, etc. Saturated divalent carboxylic acid adducts can be used. It can also be obtained by replacing a part of the glycol component used in the unsaturated polyester with glycol adducts of dicyclopentadiene or hydroxydicyclopentadiene.

The room temperature curable resin composition preferably also contains a curing agent such as ketone peroxide, such as acetylacetone peroxide (AAPO), methyl ethyl ketone peroxide (MEKPO), diethyl ketone peroxide, methyl propyl ketone peroxide. , Methyl isobutyl ketone peroxide, methyl acetoacetate peroxide, ethyl acetoacetate peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, etc. it can. In addition, you may use together other hardening | curing agents other than a ketone peroxide, for example, cumene hydroxy peroxide.
The amount of the ketone peroxide used is preferably 3 parts by weight for the upper limit and 0.5 parts by weight for the lower limit with respect to 100 parts by weight of the unsaturated polyester resin. Even if it exceeds 3 parts by weight, the effect of the unsaturated polyester resin as a curing agent may not be sufficiently exerted compared to the amount used, and if it is less than 0.5 part by weight, the room temperature curable resin composition will be There is a possibility that it will not be sufficiently cured, and there is a possibility that the amount of formaldehyde emission cannot be reduced sufficiently. A more preferred upper limit is 2 parts by weight and a lower limit is 1 part by weight. Moreover, a preferable range is 0.5-3 weight part with respect to 100 weight part of unsaturated polyester resin, and a more preferable range is 1-2 weight part.

The room temperature curable resin composition preferably further contains an air drying property imparting agent (air drying property imparting agent). The air-drying imparting agent is deposited on the surface of a film or molded product formed from the resin composition when the unsaturated polyester resin is cured, and forms a barrier layer with air on the surface, thereby It has an action of preventing oxygen from inhibiting radical polymerization of the unsaturated polyester resin and improving the drying property of the unsaturated polyester resin. By using this, the amount of formaldehyde emitted from the cured product can be further sufficiently reduced. Examples of such air dryness imparting agents include waxes described in the following (1) to (3).

(1) Natural waxes include, for example, plant waxes such as candelilla wax, carnauba wax, rice wax, wood wax, jojoba oil; animal waxes such as beeswax, lanolin, whale wax; montan wax, ozokerite, ceresin, etc. And mineral waxes such as paraffin wax, microcrystalline wax and petrolatum.
(2) Examples of synthetic waxes include synthetic hydrocarbons such as Fischer-Tropsch wax and polyethylene wax; modified waxes such as montan wax derivatives, paraffin wax derivatives, and microcrystalline wax derivatives; derivatives of animal fats and oils; And hydrogenated waxes such as hardened castor oil and hardened castor oil derivatives; fatty acids having 12 or more carbon atoms such as stearic acid, dodecanoic acid and octadecyl stearate; and derivatives thereof; alkylphenyls and higher alcohols, ethylene Examples include alcohols to which alkylene oxides such as oxide and propylene oxide are added.
(3) Examples of other materials include blended waxes such as natural wax and synthetic wax.
These may be used alone or in combination of two or more. The waxes may contain other components.
Among these, it is preferable to use paraffin wax.

As the air-drying imparting agent, it is preferable to use one or two or more types having a melting point of 40 to 80 ° C. Thereby, in the construction of the resin composition, it becomes easy to deposit on the surface of the film or molded product formed from the resin composition in the middle of curing, so that a barrier layer with air is sufficiently formed, and the effects of the present invention Can be sufficiently exhibited. In addition, it is possible to sufficiently and reliably exert additional properties such as mechanical properties such as water resistance after drying and followability to the substrate, load resistance and wear resistance, chemical resistance and long-term durability. Become.
If the melting point of the air-drying imparting agent is less than 40 ° C, the air-drying imparting agent may not be sufficiently deposited on the surface of the coating film or molded product during curing, and if it exceeds 80 ° C, the resin composition There is a risk that it cannot be sufficiently dissolved in the product. More preferably, it is 50-70 degreeC.

The air dryness imparting agent may further be composed of two or more air dryness imparting agents having different melting points. In the construction of the resin composition, the temperature conditions at the time of construction differ depending on the season, but by using two or more kinds of air-drying imparting agents having different melting points, room temperature curability and surface drying are improved throughout the year. It becomes possible to exert the effect. That is, in order to make it easier to form a barrier layer on the surface of a coating or molded product during curing, it is better to increase the melting point of the air-drying agent in summer when the temperature is high, and the air-drying agent is used in winter when the temperature is low. Although it is better to lower the melting point, a combination of an air-drying imparting agent with a high melting point and an air-drying imparting agent with a low melting point forms a sufficient barrier layer on the surface of the coating or molded product during curing regardless of the temperature. Will be.

As for the usage-amount of the said air-drying imparting agent, it is preferable that an upper limit is 1 weight part and a minimum is 0.001 weight part (10 ppm) with respect to 100 weight part of unsaturated polyester resins. If it exceeds 1 part by weight, it cannot be sufficiently dissolved in the resin composition, and the adhesion to other layers and the like may not be sufficient. If it is less than 0.001 part by weight, excellent barrier properties and curability cannot be exhibited, and workability may be significantly delayed. A more preferred upper limit is 0.3 parts by weight, and a lower limit is 0.01 parts by weight (100 ppm). Moreover, a preferable range is 0.001-1 weight part, and a more preferable range is 0.01-0.3 weight part.

In the said normal temperature curable resin composition, the accelerator for hardening at normal temperature, the acceleration adjuvant, etc. may be included as needed.
Examples of the accelerator include metal soaps such as cobalt naphthenate, manganese naphthenate, copper naphthenate, potassium naphthenate, calcium naphthenate, cobalt octylate, etc. Among them, it is preferable to use a cobalt salt. is there.
The amount of the accelerator used is preferably 0.01 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the unsaturated polyester resin. More preferably, it is 0.2 parts by weight or more and 1.0 part by weight or less.

Examples of the accelerator aid include β-ketoesters such as amines such as dimethylaniline, N, N-dimethyltoluidine, N, N-diethylaniline, N, N-di (hydroxy) -4-methylaniline, β -Ketoamides; β-diketones such as acetylacetone are preferred. Alicyclic amines also act as accelerating aids.
The total amount of the promoter aid is preferably 0.01 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the unsaturated polyester resin. More preferably, it is 0.03 weight part or more and 1.0 weight part or less.

In the above room temperature curable resin composition, further, if necessary, a filler, a thixotropic agent, a polymerization inhibitor, an antifoaming agent, a thickener, an inorganic aggregate, an inert powder, an ultraviolet absorber, a low shrinkage. Additives such as colorants such as agents, anti-aging agents, plasticizers, flame retardants, stabilizers, and pigments and toners may be included.
In the above additive, examples of the filler include aluminum hydroxide (ATH), calcium carbonate, calcium sulfate, barium sulfate, alumina, clay, talc, glass powder, milled fiber, cristobalite, mica, silica, river sand, diatomaceous earth, Inorganic fillers such as mica powder, gypsum, and glass powder; one type or two or more types of organic fillers may be mentioned. As a usage-amount of a filler, it is preferable that it is 20 to 300 weight part with respect to 100 weight part of unsaturated polyester resin.
Examples of the thixotropic agent include fumed silica. The amount of the thixotropic agent used is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the unsaturated polyester resin.

Examples of the polymerization inhibitor include hydroquinones such as hydroquinone and methylhydroquinone; benzoquinones such as benzoquinone and methyl-p-benzoquinone; catechols such as t-butylcatechol; 2,6-di-t-butyl-4 -Phenols such as methylphenol and 4-methoxyphenol; phenothiazine and the like are preferred.
As the antifoaming agent, in addition to silicon-based ones, commercially available polymer-based anti-sagging agents and other additives can be used.
As the thickener, polyvalent metal oxides such as magnesium oxide, calcium oxide and zinc oxide; polyvalent metal hydroxides such as magnesium hydroxide and calcium hydroxide; polyfunctional isocyanates and the like are suitable.
As the inorganic aggregate, inorganic powders such as silica sand, silica, clay, bentonite, aluminum hydroxide, alumina, talc, calcium carbonate and the like are suitable. Examples of the inert powder include thermoplastic resins such as polyethylene, polypropylene, and polystyrene, cured thermosetting resins such as acrylic resin, polyester resin, phenol resin, and urethane resin, and powder and / or pulverized material such as rubber and wood. Etc. are suitable.

Since the construction method of the waterproof composite covering of the present invention is configured as described above, the waterproof performance such as drainage, heat insulation, weather resistance, water resistance, fire resistance, etc., heat insulation performance, smoothness, etc. In addition to being excellent, it is possible to effectively line up, and it is possible to sufficiently suppress the possibility of causing sanitary problems by sufficiently reducing the amount of formaldehyde emission. Veranda, balcony, flat roof, floor surface It is useful as a lining method for flat surfaces of architectural spaces such as

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

(Synthesis Example 1)
A four-necked flask equipped with a thermometer, stirrer, inert gas blowing tube and reflux condenser was charged with 8 mol of triethylene glycol, 2.3 mol of propylene glycol, 4.5 mol of isophthalic acid, and 3 mol of adipic acid. Then, condensation reaction was performed until the acid value was 10 at 210 ° C. while blowing nitrogen gas. Cooled to 150 ° C., charged with 2.5 moles of maleic anhydride, heated to 210 ° C. and condensed for 15 hours with 65 parts of unsaturated polyester having a double bond titer of 996, 35 parts of styrene, 0.01 of hydroquinone An unsaturated polyester resin (A-1) having a number average molecular weight of 4,300, an acid value of 7, and a viscosity of 8 poise (1 poise = 1 × 10 ⁻¹ Pa · s) was obtained.

(Synthesis Example 2)
In the same reaction apparatus as in Synthesis Example 1, 10.3 mol of diethylene glycol, 3 mol of terephthalic acid, and 5.5 mol of phthalic anhydride were charged, and a condensation reaction was performed at 220 ° C. to an acid value of 10 while blowing nitrogen gas. Cooled to 150 ° C., charged with 1.5 mol of fumaric acid, heated to 215 ° C. and condensed for 15 hours, 60 parts of unsaturated polyester having a double bond titer of 1545, 40 parts of styrene and 0.01 part of hydroquinone Was added to obtain an unsaturated polyester resin (A-2) having a number average molecular weight of 4,500, an acid value of 7, and a viscosity of 4 poise.

(Comparative Synthesis Example 1)
In the same manner as in Synthesis Example 1, 5 mol of diethylene glycol, 5.5 mol of ethylene glycol, 4 mol of phthalic anhydride, and 6 mol of maleic anhydride were charged into a four-necked flask and condensed at 210 ° C. for 15 hours while blowing nitrogen gas. 30 parts of styrene and 0.01 part of hydroquinone were added to 70 parts of the unsaturated polyester having a double bond strength of 312 reacted to obtain an unsaturated polyester resin B having an acid value of 25 and a viscosity of 6.5 poise.

[Evaluation of cured material properties of each synthetic resin]
To 100 parts of each synthetic resin, 0.5 part of cobalt octenoate (8% metal content) and 1 part of Kayamek M (manufactured by Kayaku Akzo Co., Ltd.) are added and mixed, and the resin cured product is added according to JIS K6919 (1992). A template was produced.
The tensile strength and elongation were measured according to JIS K7113 (1995), and the deflection temperature under load was measured according to JIS K7191-1 (1996). The results are shown in Table 2.

Examples 1-4, Comparative Examples 1-4
[Fireproof and dent test]
(Preparation of test piece)
Gradient insulation (A = 15 mm, B = C = 500 mm, D = 20 mm) formed using a polystyrene foam as shown in FIG. θ = 1/100), and a calcium silicate plate of 500 mm × 500 mm, JIS A5430 (2001), thickness 10 mm, bulk specific gravity 0.8 is placed on a steel wood screw (length 16 mm). The heat insulating material with a gradient and the calcium silicate plate were fixed with a steel wood screw (length: 32 mm). After applying and drying a urethane primer on a calcium silicate plate, 5 parts by mass paraffin wax is added to 100 parts of each synthesized resin in the amount shown in Table 3, and 0.5 part of cobalt octenoate (metal content: 8%) The alicyclic amines shown in Table 3 and 1 part of Kayamek M (manufactured by Kayaku Akzo) were added and adjusted, and laminated with 2 plies of glass mat # 380 (CM-385FA; manufactured by Asahi Fiber Co., Ltd.).
Furthermore, as a finishing material, an unsaturated polyester resin finishing material having a formaldehyde emission amount measured by JIS K5601-4-1 (2003) of 0.12 mg / L or less “JOLIETHES JE-2080” (trade name, manufactured by Aika Kogyo Co., Ltd.) ) To 100 parts, 1 part of Kayamek M was added, and 125 g was applied with a brush.
(test)
The fireproof test was simply carried out by placing one fire type similar to the test conforming to Article 22 of the Building Standards Act on the above-mentioned 500 mm × 500 mm test piece and sending the wind with a fan.
In the dent test, each test piece was placed in a dryer at 60 ° C. for 1 hour, and a 500 g iron ball was dropped from a height of 1 m, and dents and cracks on the surface were visually confirmed. These results are shown in Table 3.

[Measurement of formaldehyde emission (emission)]
(Preparation of test piece)
After applying a urethane primer on a calcium silicate plate of 150 mm x 150 mm, JIS A5430 (2001), thickness 10 mm and bulk specific gravity 0.8, 5 parts by mass paraffin wax was dissolved in styrene by heating in 100 parts of each synthesized resin. The paraffin wax solution was added in the amount shown in Table 3, 0.5 part of cobalt octenoate (metal content 8%), alicyclic amine shown in Table 3, and Kayamek M (manufactured by Kayaku Akzo) 1 The glass mat # 380 (CM-385FA; manufactured by Asahi Fiber Co., Ltd.) 2 plies was laminated.
Furthermore, as a finishing material, an unsaturated polyester resin finishing material having a formaldehyde emission amount measured by JIS K5601-4-1 (2003) of 0.12 mg / L or less “JOLIETHES JE-2080” (trade name, manufactured by Aika Kogyo Co., Ltd.) ) To 100 parts, 1 part of Kayamek M was added, and 12 g was applied with a brush.
These test pieces were stored in a thermostat at 23 ° C. for 7 days.
(Measurement)
The formaldehyde emission amount of the test piece was measured by a desiccator method according to JIS K5601-4-1 (2003). The results are shown in Table 3.

Examples 5-6, Comparative Examples 5-6
[Adhesion evaluation]
(Adjustment of paraffin wax)
The synthesis of the paraffin wax dispersion solution was performed as follows.
In a four-necked flask equipped with a thermometer, stirrer, inert gas blowing tube and reflux condenser, 1 mol of fumaric acid, 0.75 mol of bisphenol A 2EO (ethylene oxide adduct), 1,3-butane 0.55 mol of diol was charged, and 40 parts of isododecane and 0.01 part of hydroquinone were added to 60 parts of unsaturated polyester which had been subjected to a condensation reaction at 180 ° C. while blowing nitrogen gas to an acid value of 1, thereby obtaining an unsaturated polyester dispersion. .
10 parts of paraffin wax (130; manufactured by Nippon Seiwa Co., Ltd.) having a melting point of 55 ° C. and 90 parts of the previously synthesized unsaturated polyester dispersion were heated and dispersed at 70 ° C. to prepare a paraffin wax dispersion having a wax concentration of 10%. .

(test)
After applying and drying a urethane primer on a normal plywood having a thickness of 9 mm as defined in 500 mm × 500 mm JAS, 100 parts of each synthesized resin is mixed with paraffin wax dispersion solution, alicyclic amine, cobalt octenoate (metal content 8) shown in Table 4. %) 0.5 part and 1 part of Kayamek M (manufactured by Kayaku Akzo) were added and adjusted, and a laminate was prepared with 2 plies of glass mat # 380 (CM-385FA; manufactured by Asahi Fiber). Unsaturated polyester resin finishing material "Jolieth JE-2080" with formaldehyde emission measured by JIS K5601-4-1 (2003) of 0.12mg / L or less after standing outdoors for 3, 7, 14 days 1 part of a curing agent (Kayamek M; manufactured by Kayaku Akzo Co., Ltd.) was added to 100 parts of 100 parts by name and manufactured by Aika Kogyo Co., Ltd., and then applied with a brush (500 g / m ² ).
After 24 hours of application of the top coat (finishing material), top coat adhesion was evaluated by a cross-cut method according to JIS K5400 (1990) 8.5.2 (gap spacing 2 mm, number of squares 25). The results are shown in Table 4. The adhesion evaluation table shown in JIS K5400 (1990) is shown in Table 1 above.

Example 7 and Comparative Example 7
[Construction period test]
(Process of Example 7)
A gradient heat insulating material (A = 30 mm, B = C = 1000 mm, D = 40 mm, θ = 1) formed on a 10 m ² concrete floor (base) using a polystyrene foam as shown in FIG. / 100), and a structural plywood having a thickness of 21 mm was laid in this order as a baseboard layer. On the top surface, 0.01 part of a paraffin wax solution obtained by heating and dissolving 5% by mass paraffin wax in styrene was added to 100 parts of the resin (A-1) synthesized in Synthesis Example 1, and cobalt octenoate (metal content: 8%) ) 0.5 parts, 0.3 parts of piperidine, and 1 part of Kayamek M (manufactured by Kayaku Akzo Co., Ltd.) are added and adjusted, and laminated with 2 plies of glass mat # 380 (CM-385FA; manufactured by Asahi Fiber Co., Ltd.) (See, for example, FIG. 1).

(Process of Comparative Example 7)
As shown in FIG. 5, a joist (gradient batten) having a different height is arranged on a 10 m ² concrete floor (base) by conventional woodwork, and a structural plywood having a thickness of 21 mm is used as a base plate layer. As laid in this order. On the top surface, 0.01 part of a paraffin wax solution obtained by heating and dissolving 5% by mass paraffin wax in styrene was added to 100 parts of the resin (A-1) synthesized in Synthesis Example 1, and cobalt octenoate (metal content: 8%) ) 0.5 parts, 0.3 parts of piperidine, and 1 part of Kayamek M (manufactured by Kayaku Akzo Co., Ltd.) are added and adjusted, and laminated with 2 plies of glass mat # 380 (CM-385FA; manufactured by Asahi Fiber Co., Ltd.) did.

(Comparison)
In the process of Example 7, the construction work was completed in 2 days because the construction work could be continuously performed by the waterproof construction worker. In the process of Comparative Example 7, it took one day for the joist to install the joists and the installation of the field board for providing the gradient by the woodworker. Two days were required for the construction, and the construction period was longer than the working example.

It is the cross-sectional conceptual diagram which illustrated the structure of the composite covering for waterproofing by the construction method of the composite covering for waterproofing of this invention. It is a cross-sectional conceptual diagram which illustrated the form of the heat insulating material used for the construction method of the composite covering for waterproofing of this invention. (A) is a heat insulating material with a gradient (gradient heat insulating material for drainage grooves) having a small inclination angle. (B) is a heat insulating material with a gradient (a heat insulating material with a gradient for flat fields) having an inclination angle and a thickness larger than those of (a). (C) is a gradient heat insulating material (flat heat insulating material for a flat field) having a larger thickness than (b) and the same inclination angle as (b). (D) is a heat insulating material (flat surface heat insulating material) having no inclination angle. In the construction method of the waterproof composite coating of this invention, it is a conceptual diagram showing an example of the formation method of a gradient heat insulation layer with time. It is the conceptual diagram used in order to demonstrate an example of the fixing method of the heat insulating material which forms a gradient heat insulation layer in the construction method of the composite covering for waterproofing of this invention. In the conventional waterproof construction method, it is a cross-sectional conceptual diagram which showed the form at the time of providing a gradient using a joist on a base | substrate.

Explanation of symbols

1: Substrate 2: Inclined heat insulating layer (heat insulating material)
3: Base plate layer or incombustible layer 4: Fiber reinforced resin layer 5: Finishing material layer 6: Drain 7: Gradient heat insulating material 8 shown in FIG. 2 (a) 8: Gradient heat insulating material 9 shown in FIG. 2 (c): Insulating material 10 with a gradient shown in FIG. 2 (b): Insulating material 11 having no inclination angle shown in FIG. 2 (d): Fixing bracket 12: Resin putty 13: joist (gradient batten)
14: Insulation (no gradient)
θ: Inclination angle A of the gradient heat insulating material A: Dimension B of the gradient heat insulating material shown in FIG. 2C: Dimension C of the gradient heat insulating material shown in FIG. 2C: With the gradient shown in FIG. Dimension D of heat insulating material: Dimension of heat insulating material with gradient shown in FIG.

Claims (3)

It is a construction method of a waterproof composite covering formed by laminating at least an inclined heat insulating layer, a base plate layer, a fiber reinforced resin layer, and a finishing material layer in this order,
The construction method of the waterproof composite covering is a method of constructing a finishing material layer without performing a ground treatment for expressing adhesiveness after at least 3 days have elapsed since the fiber reinforced resin layer was formed.
The fiber reinforced resin layer is composed of a room temperature curable resin composition containing an unsaturated polyester having a double bond titer of 300 to 1800, a polymerizable monomer and an alicyclic amine,
The room temperature curable resin composition has a tensile strength in a cured product of greater than 10 MPa and a tensile elongation of greater than 10%. The room temperature curable resin composition further contains paraffin wax.
The construction method of the composite covering for waterproofing of Claim 1 characterized by the above-mentioned. The sheathing Itaso the method of constructing the waterproofing composite coating of claim 1 or 2, characterized in that the non-combustible layer.

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