JP4237670B2 - 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 the waterproof composite covering is a waterproof construction method having high strength, high surface hardness, excellent durability, dimensional stability, etc., such as a building space represented by a veranda, balcony, flat roof, floor surface, etc. It is attracting attention as a lining method for flat surfaces. In such a waterproof construction method, it is generally performed to apply cement mortar as a finishing material in order to impart a fire spread prevention effect and the like. However, when cement mortar is used, the adhesive force is not sufficient, and because the weight is large, peeling, cracking, floating, etc. may occur due to differences in the thermal expansion of the base material after time, If the construction is not appropriate, it may come off. Furthermore, since shrinkage due to drying is large, it is necessary to proceed with work while paying attention to the drying time, and high skill is required for construction. Therefore, it is possible to absorb the difference in thermal expansion of the adherend and the movement of the base body without requiring high skills for construction, and to impart excellent non-combustibility performance, and there is a construction method that can be suitably used in renovation and the like. It is desired.

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 non-combustible composite fiber reinforced plastic (FRP) panel is disclosed in which a fiber reinforced plastic layer is formed on a graded base material, and a non-combustible material layer is formed on the fiber reinforced plastic layer (for example, patents). Reference 1). (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, there is room for contrivance for waterproofing that can sufficiently prevent sanitary problems in cured products and that can more easily exhibit nonflammability.
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 waterproofing performance and non-combustion performance such as weather resistance and water resistance, and can be efficiently lined, and the amount of formaldehyde emission is sufficiently reduced. It is an object of the present invention to provide a construction method for a waterproof composite covering capable of sufficiently suppressing the possibility of causing sanitary problems.

The inventors of the present invention have made various studies on the waterproof lining method, and paid attention to the fact that the ceramic plate can exhibit heat resistance and fire resistance. By arranging the ceramic plate in the uppermost layer of the waterproof composite covering, It is found that a waterproof composite covering excellent in heat resistance and fire resistance can be obtained, and if it is a construction method in which at least a fiber reinforced resin layer and a ceramic layer are laminated in this order on a substrate, high skill is not required. It has been found that excellent waterproof performance and non-combustible performance can be imparted easily and in a short period of time. 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. The present inventors have found that the body construction method is very useful as a lining method for a flat part of an architectural space and the like, and arrived at the present invention by conceiving that the above problems can be solved brilliantly. 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 coating comprising at least a fiber reinforced resin layer and a ceramic layer laminated in this order on a substrate, wherein the fiber reinforced resin layer has a double bond strength of 300. It is comprised by the normal temperature curable resin composition containing unsaturated polyester which is -1800, a polymerizable monomer, and an alicyclic amine, The said normal temperature curable resin composition is larger than 10 MPa in tensile strength in hardened | cured material, And it is a construction method of the composite covering for waterproofing whose tensile elongation rate is a thing larger than 10%.
The present invention is described in detail below.

The construction method of the waterproof composite coating according to the present invention is obtained by laminating at least a fiber reinforced resin layer and a ceramic 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.
In addition, when a base | substrate is concrete, asphalt, and asbestos slate, it can construct without an incombustible layer and the surface moisture content is 5 mass% or less is used suitably.

In the above construction method, a heat insulating layer may be laminated between the substrate and the fiber reinforced resin layer, and by providing the heat insulating layer, heat insulating properties, waterproof properties, moisture proof properties can be imparted or improved, and Since water tightness and mechanical strength can be made more sufficient, energy saving and indoor dew condensation prevention functions can be exhibited. A heat insulating layer protective layer such as a structural plywood is laminated between the heat insulating layer and the fiber reinforced resin layer. This protective layer may be a non-combustible layer.
The heat insulating layer that may be used in the above construction method is composed of a heat insulating material. Examples of the heat insulating material include urethane foam, vinyl chloride foam, acrylic foam, styrene-polyethylene graft mixed foam, phenol foam, polystyrene. A hard and foamable resin such as foam, carbonized cork, and foamed glass can be used.
The heat insulating layer may be provided with a gradient in order to improve the waterproofing of the construction surface.For example, the heat insulating material formed into a flat plate is used, and the thickness is continuously increased so that a constant gradient is provided on at least one surface thereof. A gradient heat insulation layer can be formed by using a material having a different thickness.
The heat insulating layer is preferably formed by fixing to the base with a screw together with a protective layer so as not to move, or by fixing each to the base with an adhesive, adhesive or tape. is there.

In the construction method, a primer layer (adhesive layer) forming step is performed as necessary. The primer layer can be formed by applying and curing the primer, but by providing the primer layer, the adhesion to the substrate or the heat-insulating protective layer serving as the foundation is further ensured, and the adhesion to the fiber reinforced resin layer is improved. It becomes possible to strengthen the property. In addition, the generation of bubbles can be sufficiently prevented by covering the base surface.
As the primer, an epoxy resin, a polyurethane resin, an unsaturated polyester resin, a vinyl ester resin, an acrylic resin, a urethane acrylate resin, and the like are suitable, and known ones can be used. The coating amount is preferably 0.1 to 1 kg / m ^2, and it is preferable to increase the coating amount or apply twice as necessary for the portion where the primer is sucked heavily. In addition, about the coating method and hardening conditions of a primer, it is the same as that in the fiber reinforced resin layer mentioned later.

Moreover, in order to improve followability with a base | substrate after hardening of the said primer, you may apply | coat 0.1-2 kg / m < ² > of soft resin. As the soft resin, an unsaturated polyester resin, an epoxy resin, a polyurethane resin, a urethane acrylate resin, or the like is suitable. The cured product has a tensile elongation percentage of more than 10%, preferably 30 to 300. % Is preferred. In addition, in order to improve 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.

Next, in the construction method, a fiber reinforced resin (FRP: Fiber Reinforced Plastics) layer forming step is performed. 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, but as the fibrous reinforcing material, glass fiber, metal fiber, One type or two or more types such as ceramic fiber and carbon fiber can be used, and the shape includes one or more types such as chopped strand mat, cloth (woven fabric), nonwoven fabric, and 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. A preferable range is 0.01 to 3 parts by weight, and a more preferable range is 0.05 to 1.5 parts by weight. 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 300% 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, next, the ceramic layer forming step will be performed, but when constructing the ceramic layer, in order to protect the underlying fiber reinforced resin layer from alkaline components, it is finished as necessary. It is desirable to apply 0.2 to 1 kg / m ^{2 of} material (top coat). The finishing material is composed of, for example, a resin composition containing one or more of paints such as fluorine, acrylic silicon, and acrylic urethane, unsaturated polyester resin, urethane resin, epoxy resin, acrylic resin, and vinyl ester resin. In addition, pigments and the like can be added and colored as necessary. 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.
A preferred form of such a resin composition is to include an unsaturated polyester resin comprising an unsaturated polyester and a polymerizable monomer.

The ceramic layer will be provided in the uppermost layer of the waterproof composite coating, which can give or improve not only excellent fireproofing performance and nonflammability, but also heat insulation, waterproofing and moistureproofing. It is possible to respond sufficiently even when non-combustibility is required by the Building Standard Law. Such a ceramic layer is composed of a ceramic plate, and for example, concrete, brick, glass, rock, wood wool cement plate, gypsum board, calcium silicate plate, porcelain tile and the like are preferably used. Among these, in view of being provided in the uppermost layer, those having high cosmetic properties are preferable.
As a method for forming the ceramic layer, it is preferable that the ceramic layer is formed by applying a wedge or the like so that there is no movement, and then laying it without gaps, and then removing and fixing the wedge. Further, it may be fixed to the base with a screw, or may be fixed to the base with an adhesive, an adhesive, or a tape. In addition, it is preferable to chamfer the entrance corner and the exit corner. As described above, in the construction method of the present invention, a layer exhibiting fire prevention performance and cosmetics can be formed easily and in a short period without requiring a high technique, and thus can be suitably applied to home renovation and the like.

Further, in order to fix the ceramic layer so as not to slip, an inorganic aggregate may be sprayed to make the surface rough when forming the fiber reinforced resin layer. Specifically, when forming the fiber reinforced layer or the finish layer on the fiber reinforced layer, the surface is formed by spraying inorganic aggregate on the surface of the uncured fiber reinforced layer or finish layer and curing it.

Hereinafter, an example of a method for forming the ceramic layer will be described with reference to the drawings, but the present invention is not limited thereto.
As a ceramic board, it is preferable to change a shape according to the place to construct, for example, the thing for flat fields as illustrated in FIG. 2 (a), and drainage as illustrated in FIG. 2 (b) It can be used in combination with a side groove for covering the groove.
First, as shown in FIG. 3, after the fiber reinforced resin layer 3 is formed (or after finishing layer 10 is cured when further finishing material is applied), a spacer 8 made of water-resistant urethane foam or the like is formed in the side groove portion. Are arranged at equal intervals. Then, the wedge 9 is applied, the side groove ceramic plate 7 and the flat ceramic plate 6 are arranged and pressed from above, and the whole is laid so that there is no gap. Finally, the wedge 9 is removed, and the corner portion is fixed with a sealing material. Thus, a ceramic layer can be formed. If the fiber reinforced resin layer 3 or the finishing layer 10 has unevenness and the ceramic plate is not stable, the unevenness adjusting adhesive or the adhesive tape 5 may be stuck so that the end portions of the ceramic plates are in contact with each other. . In addition, the structure in this invention after forming a ceramic layer is notionally shown in FIG.
Further, at the rising portion of a parapet or the like, the flat plate ceramic plate may be pressed and fixed, or may be fixed using an adhesive or a screw.

According to the construction method of the waterproof composite coating of the present invention, in addition to excellent mechanical properties such as non-flammability, waterproofness, heat insulation, water resistance, followability to the substrate, load resistance, and wear resistance, It is possible to obtain a waterproof composite covering that has additional performance such as chemical properties and long-term durability, and that can sufficiently reduce the amount of formaldehyde emission after curing and curing. The waterproof composite covering constructed by the construction method 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 finishing material 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. A preferable range is 0.5 to 3 parts by weight with respect to 100 parts by weight of the unsaturated polyester resin, and a more preferable range is 1 to 2 parts by weight.

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) Examples of natural waxes include plant waxes such as candelilla wax, carnauba wax, rice wax, wood wax and jojoba oil; animal waxes such as beeswax, lanolin and whale wax; montan wax, ozokerite and ceresin Mineral wax; paraffin wax, microcrystalline wax, petrolatum and the like.
(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 possibility 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). A preferred range is 0.001 to 1 part by weight, and a more preferred range is 0.01 to 0.3 part by weight.

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 according to the present invention is configured as described above, fireproof performance such as incombustibility, drainage, heat insulation, weather resistance, water resistance, fire resistance, waterproof performance, smoothness, etc. In addition to being aesthetically pleasing, it can be lined efficiently, and the amount of formaldehyde emission can be sufficiently reduced to sufficiently suppress the risk of sanitary problems, making it a 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 1.

Examples 1-4, Comparative Examples 1-4
[Fireproof and dent test]
(Preparation of test piece)
500 parts by weight of paraffin wax in an amount shown in Table 2 is added to 100 parts of each resin synthesized on an ordinary plywood having a thickness of 9 mm defined by 500 mm × 500 mm JAS, and 0.5 part of cobalt octenoate (8% metal content). The alicyclic amine shown in Table 2 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.). Then, after the resin composition was dried, a calcium silicate plate having a size of 500 mm × 500 mm, JIS A5430 (2001), a thickness of 10 mm, and a bulk specific gravity of 0.8 was fixed using a commercially available double-sided adhesive tape.
(test)
The fireproof test was simply carried out by putting one of the same fire types as the test conforming to the standard related 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. The results are shown in Table 2.

[Measurement of formaldehyde emission (emission)]
(Preparation of test piece)
150 mm x 150 mm JAS-specified 9 mm thick F ☆☆☆☆ After applying a urethane primer on a normal plywood and drying, a paraffin wax solution in which 5% by weight paraffin wax is dissolved in styrene by heating is displayed on 100 parts of each synthesized resin. 2, 0.5 parts of cobalt octenoate (metal content 8%), alicyclic amines shown in Table 2, and 1 part of Kayamek M (made by Kayaku Akzo) are added and adjusted. And a glass mat # 380 (CM-385FA; manufactured by Asahi Fiber Co., Ltd.) 2 plies. And after this resin composition dried, the calcium silicate board of 150 mm x 150 mm, JIS A5430 (2001), thickness 10mm, and bulk specific gravity 0.8 was fixed using the commercially available double-sided adhesive tape.
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 2.

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 the conceptual diagram which illustrated one form of the ceramic board used for the construction method of the composite covering for waterproofing of this invention. (A) is a ceramic plate for flat fields. (B) is a ceramic plate for side grooves capable of forming a drainage groove. It is the conceptual diagram used in order to demonstrate an example of the formation method of a ceramic layer in the construction method of the composite covering for waterproofing of this invention.

Explanation of symbols

1: Substrate 2: Primer layer 3: Fiber reinforced resin layer 4: Ceramic layer (ceramic plate)
5: Non-land surface adjustment adhesive or adhesive tape 6: Flat plate ceramic plate 7 shown in FIG. 2A: Flat plate ceramic plate 8 shown in FIG. 2B 8: Spacer 9: Wedge 10: Finish layer

Claims (2)

A construction method for a waterproof composite coating comprising at least a fiber-reinforced resin layer and a ceramic layer laminated in this order on a substrate,
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 , an alicyclic amine, and a paraffin wax ,
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 amount of the alicyclic amine used is 0.01 to 1.5 parts by weight with respect to 100 parts by weight of an unsaturated polyester resin comprising an unsaturated polyester and a polymerizable monomer. Construction method of the composite covering for waterproofing as described in 2.

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