JP4250557B2 - 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, a fiber reinforced resin layer is formed on a base material such as a wood material or a concrete structure, and an improvement in weather resistance such as weather resistance and water resistance and smoothness is provided on the upper layer. This is done by providing a finishing material layer for the purpose. In particular, in recent waterproofing construction, there is an increasing need for design design, and various technologies that can exhibit not only basic performance such as durability, weather resistance, waterproofness, strength, but also excellent design properties have been studied. ing.

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.

Conventional construction techniques in the construction field include (a) a polymerizable unsaturated monomer, (b) a polymer that is soluble or dispersible in the component (a), (c) a radical polymerization initiator, and (d) transition. The present invention relates to a radical polymerization curable construction material composition containing a metal soap and (e) a compound that forms a complex or chelate with the transition metal in the component (d). A composition containing butylamine is disclosed (for example, see Patent Document 1). In this composition, the compound (e) such as dibutylamine is used for the purpose of delaying the polymerization initiation reaction in the polymerization and curing system. However, this technology is intended to reinforce concrete structures, and by suppressing the amount of formaldehyde emitted to a lower level so that it can fully respond to partial revisions of the Building Standards Act, etc. In addition, the possibility of causing sanitary hindrance in the curing process and cured product of the resin composition is sufficiently suppressed, and there is room for contrivance to provide a waterproof composite covering with excellent design properties.
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 weather resistance and water resistance, and in aesthetics such as design properties, and can be efficiently lined, and has a formaldehyde emission amount. An object of the present invention is to provide a construction method for a waterproof composite covering capable of sufficiently suppressing the risk of causing sanitary problems when sufficiently reduced.

The inventors of the present invention have made various studies on the waterproof lining construction method. As a construction method of a waterproof composite covering formed by laminating at least a fiber reinforced resin layer and a finishing material layer in this order on a substrate, Focusing on the fact that it is possible to obtain a waterproof composite covering excellent in aesthetics such as waterproof performance and smoothness, etc., and further, when the finish material layer is exposed to a granite appearance, a granite finish finish material layer, It has been found that it is possible to exhibit not only design properties but also excellent smoothness and anti-slip properties. 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. The inventors have found that the construction method is very useful as a lining method for a flat portion of an architectural space, etc., conceived that the above problems can be solved brilliantly, and have reached the present invention. 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 granite-like finishing material layer laminated in this order on a substrate, wherein the fiber-reinforced resin layer has a double bond strength. The room temperature curable resin composition contains an unsaturated polyester having a valence of 300 to 1800, a polymerizable monomer, and an alicyclic amine. The room temperature curable resin composition has a tensile strength of 10 MPa in a cured product. This is a construction method of a waterproof composite covering that is larger and has a tensile elongation of greater 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 granite finish 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.

In the above construction method, a non-combustible layer may be laminated between the base and the fiber reinforced resin layer, and the waterproof composite covering formed by laminating the non-combustible layer between the base and the fiber reinforced resin layer. This construction method is also one preferred embodiment of the present invention.
The non-combustible layer that may be used in the above construction method is composed of a non-combustible material, for example, a flat plate such as concrete, brick, glass, rock, metal, wood cement board, gypsum board, calcium silicate board, etc. Is mentioned. 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 incombustible 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. In addition, it is preferable to chamfer the entrance corner and the exit corner.

In the above construction method, a heat insulating layer may be laminated between the base and the incombustible layer or the fiber reinforced resin layer, and by providing the heat insulating layer, heat insulating properties and moisture proof properties can be imparted or improved, Energy saving and indoor 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 described above, a fiber reinforced resin (FRP) layer forming process is performed next. When the fiber reinforced resin layer is constructed, a heat insulating layer protective layer or a non-combustible layer serving as a base is provided. In order to ensure adhesion with the surface, it is preferable to apply a primer 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 substrate and the like. 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 tensile elongation of the cured product is greater than 10%, preferably 30 to 300%. Is preferred.
Moreover, in order to improve the adhesiveness with the surface of the heat insulating layer protective layer or the incombustible layer as a base, a filler such as silica sand and talc may be blended, and the amount used is 100 parts by weight of a soft resin. 50 to 300 parts by weight is preferable.

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. 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 granite-like finishing material layer is formed. The granite-like finishing material layer means a finishing material layer that expresses the granite-like appearance, and is usually finished. Any resin composition may be used as long as the hue is changed by adding particles (aggregate) to the resin composition used as the material (top coat). By adding particles (aggregate) in this way, an excellent aesthetic appearance can be exhibited, and the slip resistance can be further improved.

Examples of the resin composition used for the granite-finishing material layer include paints such as fluorine, acrylic silicon, and acrylic urethane, unsaturated polyester resins, urethane resins, epoxy resins, acrylic resins, vinyl ester resins, and the like, or Those containing two or more types are suitable, and among them, those that are curable at room temperature are preferably used. However, in order to sufficiently exhibit the aesthetics of the particles (aggregates), the resin composition must have transparency. preferable.
As the resin composition, the formaldehyde emission amount in the cured product of the resin composition is preferably 1.8 mg / L or less, similarly to the room temperature curable resin composition used in the fiber reinforced resin layer. 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.

As the granite-like finishing material layer, for example, the resin composition is applied and then particles (aggregate) are dispersed, or the resin composition is added with particles (aggregate) added in advance. It is preferable to form by hardening afterwards. The raw material, coating method, and curing method are the same as those described above for the fiber reinforced resin layer. In addition, after such a granite-like finish material layer is formed, a finishing material such as the above resin composition may be further applied, thereby imparting excellent smoothness and gloss, and having a beautiful appearance. Can be kept for a long time.
In the granite-like finishing material layer formed in this manner, the surface shape may be smooth or may have irregularities.

Examples of the particles (aggregate) used in the above-mentioned granite-finished material layer include sand, quartz sand, quartz sand, boulder gravel, pebbles, slag, those colored or fired; rocks such as quartz powder and quartz sand powder. Examples include powder, colored porcelain, and one or more of zinc white, calcium carbonate, zeolite, alumina, glass powder, glass beads, porcelain, and the like, in addition to those obtained by baking and curing a ceramic body. Moreover, 1 type (s) or 2 or more types, such as artificial stone obtained by hardening colored unsaturated polyester resin and acrylic resin syrup, an epoxy resin, and an artificial stone of a phenol resin, may be sufficient.

In the particle (aggregate), the particle size is preferably in the range of about 0.1 to 10 mm, and more preferably in the range of 0.5 to 5 mm. Two or more kinds of particles (aggregates) having different particle diameters may be used. In this case, for example, after applying the resin composition on the fiber reinforced resin layer, before curing, a large particle (particle having a larger particle size) is sprayed to form a large particle layer, It is preferable to form small particle layers by spraying small particles (particles having a smaller particle size). By spraying the small particles later in this way, a part of the small particles enter between the large particles, and the resin composition is cured in this state, so that a granite finishing material layer that is superior in strength and aesthetics is formed. It will be.

In the construction method of the waterproof composite coating according to the present invention, the granite finish finishing material layer is constructed without performing a ground treatment for developing adhesion after at least 3 days have passed since the fiber reinforced resin layer is formed. As a result, the 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 granite finish material layer, for example, a wall, a pillar, and an interior Installation, movement, etc. of materials, other fixtures and equipment can be carried out. As described above, the construction method of the waterproof composite covering for constructing the granite finish material layer without performing the ground treatment for expressing the adhesiveness after at least 3 days has passed since the fiber reinforced resin layer is formed. This is one of the preferred 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 granite finish 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 granite-like finishing material layer and the fiber reinforced resin layer are used so that the waterproof composite covering is excellent in waterproof performance such as weather resistance, water resistance, and aesthetics such as design. In order to construct in such a manner, a normal temperature curable resin composition that forms a fiber-reinforced resin layer and a resin composition that forms a granite finish material layer It is preferable to appropriately adjust the above. For example, it adjusts by mix | blending the paraffin wax etc. for improving surface drying property with the normal temperature curable resin composition which forms a fiber reinforced resin layer, and the resin composition which forms a granite-like finishing material layer. In this way, it is possible to carry out the construction usually accompanied by the construction method of the waterproof composite covering from the formation of the fiber reinforced resin layer to the formation of the granite finish material layer. The granite finish material layer is constructed so as to be in close contact with the fiber reinforced resin layer.

In the above construction method, at least 3 days after the formation of the fiber-reinforced resin layer, the granite-finished material layer is formed, and the granite-finished material layer is applied to the fiber-reinforced resin without performing a ground treatment for expressing adhesion. As the adhesion of the granite finish material layer when it is laminated on the layer, for example, the granite finish material (resin composition constituting the granite finish material layer) 3 days after the formation of the fiber reinforced resin layer 24 hours after applying the granite finish, the adhesion of the granite finish (gap spacing 2 mm, number of squares 25) is evaluated by a cross-cut method according to JIS K5400 (1990) 8.5.2. In this case, the adhesion evaluation score is preferably 6 points or more. More preferably, the adhesion evaluation score when a granite finish 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 covering of the present invention, the mechanical properties such as waterproofness, water resistance, followability to the substrate, load resistance, abrasion resistance, etc. are excellent, as well as chemical resistance and long-term durability. In addition, it is possible to obtain a waterproof composite coating that has additional performance such as design properties and that can sufficiently reduce the amount of formaldehyde emission after curing and curing. The waterproof composite covering constructed by the above is also one aspect of the present invention.

Below, the room temperature curable resin composition for forming the fiber reinforced resin layer and the room temperature curable resin composition suitable as the resin composition used for the granite finish material layer will be further described.
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) 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 coating of the present invention is configured as described above, it is excellent in waterproof performance such as weather resistance, water resistance, fire resistance, etc., and in aesthetics such as design, and efficiently lining. Moreover, it is possible to sufficiently suppress the possibility of causing sanitary problems by sufficiently reducing the amount of formaldehyde emitted, and architectural spaces represented by verandas, balconies, flat roofs, floor surfaces, etc. It is useful as a lining method for flat surfaces of

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 tensile 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)
500mm x 500mm JAS-regulated 9mm thick plywood, 500mm x 500mm, JIS A5430 (2001), 10mm thick, 0.8mm bulk specific gravity calcium silicate board fixed with steel wood screws (length 16mm) did.
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 amine shown in Table 3 and 1 part of Kayamek M (made by Kayaku Akzo) were added and adjusted, and laminated with 2 plies of glass mat # 380 (CM-385FA; made by Asahi Fiber). A fiber reinforced resin layer was formed.

The thus formed fiber reinforced resin layer (after curing) is an unsaturated polyester resin having a formaldehyde emission amount measured by JIS K5601-4-1 (2003) of 0.12 mg / L or less [granulated finishing material “ "Joryse JE-2081" (trade name, manufactured by Aika Kogyo Co., Ltd.)] 125 g of Kayamek M1 added to 100 parts was applied with a brush.
(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.
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 and drying a urethane primer on a calcium silicate plate having a size of 150 mm × 150 mm, JIS A5430 (2001), thickness 10 mm, and bulk specific gravity 0.8, 5 mass% paraffin wax was dissolved in styrene by heating in 100 parts of each synthesized resin. Paraffin wax solution was added in the amount shown in Table 3, and 0.5 part of cobalt octenoate (8% metal content), alicyclic amine shown in Table 3, and 1 part of Kayamek M (manufactured by Kayaku Akzo) were added. The fiber reinforced resin layer was formed by laminating with 2 plies of glass mat # 380 (CM-385FA; manufactured by Asahi Fiber Co., Ltd.).

The thus formed fiber reinforced resin layer (after curing) is an unsaturated polyester resin having a formaldehyde emission amount measured by JIS K5601-4-1 (2003) of 0.12 mg / L or less [granulated finishing material “ "Jolie's JE-2081" (trade name, manufactured by Aika Kogyo Co., Ltd.)] 100 g of Kayamek M1 part added thereto was applied with 12 g of 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 2EO (ethylene oxide adduct) of bisphenol A, 1,3-butane Charged 0.55 mol of diol and added 40 parts of isododecane and 0.01 part of hydroquinone to 60 parts of unsaturated polyester which was condensed at 180 ° C. to an acid value of 1 while blowing nitrogen gas to obtain an unsaturated polyester dispersion. It was.
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 having a formaldehyde emission amount of 0.12 mg / L or less as measured by JIS K5601-4-1 (2003) after being left outdoors for 3, 7, 14 days [Granit-finished finishing material “Jolies JE- 2081 "(trade name, manufactured by Aika Kogyo Co., Ltd.)] To 100 parts, 1 part of a curing agent (Kayamek M; manufactured by Kayaku Akzo Co., Ltd.) was added and stirred, 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.

Claims (4)

It is a construction method of a waterproof composite covering formed by laminating at least a fiber reinforced resin layer and a granite finish material layer in this order on a substrate,
The construction method of the waterproof composite covering is a method of constructing a granite-finishing material layer without performing a ground treatment for expressing adhesion after at least 3 days have elapsed after forming the fiber reinforced resin layer,
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 construction method of the waterproof composite coating according to claim 1, wherein the waterproof composite coating is formed by laminating a non-combustible layer between a base and a fiber reinforced resin layer. The room temperature curable resin composition constituting the fiber reinforced resin layer further includes paraffin wax,
3. The waterproof composite according to claim 1, wherein the amount of the paraffin wax used is 10 ppm to 500 ppm with respect to 100 parts by weight of the unsaturated polyester resin comprising the unsaturated polyester and the polymer monomer. How to apply the covering. The granite finish material layer is composed of a resin composition having a formaldehyde emission amount measured by JIS K5601-4-1 (2003) in a cured product of 1.8 mg / L or less. The construction method of the composite covering for waterproofing in any one of Claims 1-3.