JP2005344235A - Water proof and durable roofing sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a roofing sheet excellent in waterproof durability, weatherability, flexibility and sewing workability. <P>SOLUTION: The roofing sheet comprises a ground fabric, a first adhesive layer impregnated and fixed to the ground fabric, containing a fluorine-containing compound, an isocyanate compound and one or more species of crosslinking agent selected from coupling agents and formed by crosslinking the layer and a second adhesive layer formed on the first layer, containing a coupling agent and formed by crosslinking the layer. The sheet has a fluorine-containing layer formed at least on one side of the ground fabric and is excellent in waterproof durability. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a waterproof sheet excellent in durability, weather resistance, flexibility and sewing workability. More specifically, the present invention relates to a waterproof sheet that is less likely to deteriorate in product strength even under high temperature and high humidity, has excellent shape stability, and is suitable for a roofing sheet or the like.

As roof and roof waterproofing materials, there are asphalt waterproofing, sheet waterproofing, paint film waterproofing, exterior wall paint waterproofing material, stainless steel waterproof roofing material, etc. Among them, asphalt waterproofing material accounts for the majority of the market share. However, since the useful life of these waterproofing materials is about 10 to 20 years, it is difficult to repair 60 years, which is the life of the building, without repair.
In recent years, buildings have become more durable and various methods have been developed to reduce the number of repairs. Among them, a highly durable sheet waterproof material has been used. This is a waterproof sheet in which a glass fiber fabric is impregnated with a tetrafluoroethylene resin, and is also used as a permanent membrane material in sports facilities and permanent facilities.

Tetrafluoroethylene resin is used in various applications taking advantage of excellent flame retardancy, antifouling properties, durability, etc., but on the other hand, its crystallinity is high and the product becomes rigid. In addition, various difficulties have been pointed out, such as being chemically inert and difficult to process, bond and handle due to its high melting point.
For example, a waterproof sheet obtained by impregnating a glass fiber fabric with an ethylene tetrafluoride resin has poor flexibility when used as a roofing / roofing material, and thus has a problem in workability. Furthermore, at the time of bonding work, it is necessary to melt at a high temperature of 327 ° C. or higher, which is a melting point, and there are problems in workability and safety.

Moreover, as a means for repairing the roof / rooftop waterproofing material, JP-A-11-310999 (Patent Document 2), JP-A-2000-17790 (Patent Document 3), and JP-A-2003-129617 (Patent Document). 4) discloses a laminate including a fluororesin and an aluminum foil. However, the laminate is not used in a waterproof body for the purpose of repairing a partial defect of the waterproof material. Furthermore, there is a drawback that durability due to peeling between the fluororesin layer and the aluminum foil layer is insufficient.
Therefore, as a means for improving the adhesion of the waterproof sheet, Japanese Patent Publication No. 62-34324 (Patent Document 1) discloses a method for producing a low melting point fluororesin copolymer. Since this resin has a low melting point, it can be formed into a film by calendar molding or extrusion molding, and further used as a raw material for waterproof sheets by laminating on a fiber base fabric. However, although it is excellent in antifouling property, it has a drawback that it is practically insufficient in terms of flexibility, flexibility and sewing properties (hot air welding).

  Similarly, as a method of using a low melting point fluororesin copolymer, Japanese Patent Application Laid-Open No. 2000-117896 discloses a method using a tetrafluoroethylene-hexafluoropolypropylene-vinylidene fluoride resin as in the present invention. ing. However, this method has the disadvantage that the strength of the glass fiber is extremely lowered under a high temperature and high humidity or in an environment where it comes into contact with moisture at a high temperature, resulting in poor long-term durability. Since the low-melting point resin is laminated as an inner layer, it has a drawback that the adhesive strength is greatly reduced in the high temperature part.

Sheets used as roofing materials on building roofs are exposed to wind and rain, and are exposed to the direct sunlight of the sun.Therefore, long-term durability under high temperature and high humidity and high temperature environments that come into contact with moisture, especially fiber base materials. It has been desired to provide a waterproof sheet that requires strength retention and adhesion retention with an outer layer resin, and further has sewing properties, ease of work, and flexibility.
Japanese Examined Patent Publication No. 62-34324, page 2 JP 11-310999 A, page 2 JP 2000-17790, page 2 JP 2003-129617 A, page 2 JP 2000-117896 A, pages 2 to 4

  The present invention provides a roofing sheet that is highly durable, excellent in weather resistance and flexibility, excellent in water resistance and heat resistance, and excellent in sewing properties, adhesiveness, and shape stability. In particular, the present invention provides a roofing sheet having excellent product strength retention and adhesive strength retention even under high temperature and high humidity and in a high temperature environment in contact with moisture.

The roofing sheet excellent in water resistance durability of the present invention is a laminate comprising a fiber base fabric and a fluorine-containing resin layer formed on at least one surface thereof, and between the fiber base fabric and the fluorine-containing resin layer,
A first adhesive layer that is impregnated and fixed to a fiber base fabric and includes a fluorine-containing compound and at least one cross-linking agent selected from an isocyanate compound and a coupling agent, and is formed by cross-linking;
A second adhesive layer formed on the first adhesive layer and including a coupling agent and formed by crosslinking;
Is formed.
In the roofing sheet excellent in water resistance durability of the present invention, the fluorine-containing resin layer comprises at least vinylidene fluoride, ethylene trifluoride, ethylene trifluoride chloride, ethylene tetrafluoride, propylene hexafluoride, fluoroalkyl vinyl ether And at least one fluorine-based copolymer resin composed of at least two monomers selected from ethylene.
In the roofing sheet excellent in water resistance durability of the present invention, the fluorine-containing resin layer is a mixed composition of 50 to 95% by mass of a highly rigid and highly heat-resistant fluorine-containing resin and 5 to 50% by mass of a highly elastic fluorine-containing resin. It is preferable that a thing is included.
In the roofing sheet excellent in water resistance durability of the present invention, the high-rigidity and heat-resistant fluorine-containing resin of the fluorine-containing resin contains a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer resin, And it is preferable that the melting | fusing point is 150 degreeC or more.
In the roofing sheet excellent in water resistance durability of the present invention, the highly elastic fluorine-containing resin of the fluorine-containing resin layer is a vinylidene fluoride-tetrafluoroethylene copolymer resin or a vinylidene fluoride-hexafluoroethylene copolymer. It is preferable to include at least one selected from a resin, a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer resin.
In the roofing sheet excellent in water resistance durability of the present invention, the highly elastic fluorine-containing resin of the fluorine-containing resin layer contains a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer resin, and It is also preferable that the melting point is 140 ° C. or lower.
In the roofing sheet excellent in water resistance durability of the present invention, each of the first adhesive layer and the second adhesive layer contains a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer resin as a binder. It is preferable.

  The roofing sheet with high water resistance and durability according to the present invention is excellent in flexibility and sewing properties during construction, and also has a product strength retention rate and adhesive strength even under high temperature and high humidity, and in a high temperature environment in contact with moisture. Therefore, it is useful as a waterproof sheet for roofs and rooftops.

Embodiments of the durable roofing sheet of the present invention are shown in FIGS.
In the water-resistant and durable roofing sheet of the present invention shown in FIG. 1, a first adhesive layer that is cross-linked and contains a fluorine-containing compound, an isocyanate compound, and a coupling agent on both surfaces of the glass fiber base fabric 1-1. 2, a second adhesive layer 3 formed by cross-linking including a coupling agent, and a fluorine-containing resin layer 4-1 are sequentially formed.
In the water-resistant durable roofing sheet of the present invention shown in FIG. 2, on the both surfaces of the glass fiber base cloth 1-1, a first adhesive layer 2 formed by crosslinking containing a fluorine-containing compound, an isocyanate compound and a coupling agent, And a second adhesive layer 3 formed by cross-linking including a coupling agent, and a fluorine-containing resin layer 4-2 made of a mixed composition of a high-rigidity, high-heat-resistant fluorine-containing resin and a highly elastic fluorine-containing resin. ing.
In the water-resistant durable roofing sheet of the present invention shown in FIG. 3, a first adhesive layer 2 formed by cross-linking containing a fluorine-containing compound, an isocyanate compound and a coupling agent on both surfaces of the fiber base cloth 1-1. The second adhesive layer 3 including a coupling agent and crosslinked and a fluorine-containing resin layer 4-3 made of a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer are sequentially formed. .
In the water-resistant durable roofing sheet of the present invention shown in FIG. 4, a first adhesive layer 2 formed by crosslinking on both sides of a polyester fiber base fabric 1-2 containing a fluorine-containing compound, an isocyanate compound and a coupling agent. The second adhesive layer 3 including a coupling agent and formed by crosslinking, and the fluorine-containing resin layer 4-1 are sequentially formed.

The fiber base fabric used in the water-resistant durable roofing sheet of the present invention includes natural fibers such as cotton and hemp, inorganic fibers such as glass fibers, regenerated fibers such as viscose rayon and cupra, semi-synthetic fibers, For example, it is composed of at least one selected from di- and triacetate fibers and the like, and synthetic fibers such as nylon 6, nylon 66, polyester (polyethylene terephthalate, etc.) fibers, aromatic polyamide fibers, acrylic fibers, and polyolefin fibers. You can choose from fabrics.
Moreover, it is preferable that the fiber in a fabric is a long fiber yarn from the surface of intensity | strength and a flexibility. The fabric structure may be a woven fabric, a knitted fabric, or a composite thereof, but at least a coarse knitted fabric composed of yarns including warps and wefts arranged in parallel at intervals between yarns. And non-coarse knitted fabrics are preferred. For example, plain weave, twill weave, or satin weave is preferable as the base fabric structure of the coarse-textured knitted fabric and the non-rough-textured knitted fabric.

  In particular, as the fiber base fabric used in the water-resistant and durable roofing sheet of the present invention, it is desirable to use glass fiber yarns from the viewpoint of long-term durability, heat resistance, and shape stability. From the viewpoint of properties, the fiber diameter is preferably 6 μm to 13 μm and the thickness is preferably 0.3 mm to 1.0 mm. When the fiber diameter exceeds 13 μm, the flexibility and flexibility are inferior, and when the fiber diameter is less than 6 μm, the product cost is increased. When the thickness exceeds 1.0 mm, the flexibility and the handleability are inferior. When the thickness is less than 0.3 mm, the mechanical properties of the product are inferior. The glass fiber may be subjected to a silane-based or titanate-based coupling treatment according to the purpose in order to improve the adhesion with the resin to be coated.

  In the present invention, the fluorine-containing resin used in the fluorine-containing resin layer includes at least vinylidene fluoride, ethylene trifluoride, ethylene trifluoride chloride, ethylene tetrafluoride, propylene hexafluoride, fluoroalkyl vinyl ether, and ethylene. A fluorine-based copolymer resin composed of at least two monomers selected from the above is preferable. For example, tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-3 Fluorinated ethylene chloride (ECTFE), tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer, tetrafluoroethylene-vinylidene fluoride copolymer, hexafluoropropylene-vinylidene fluoride copolymer, etc. Can be used. These copolymer resins may be used alone, or two or more of them may be used as a mixed composition. Preferably, for the purpose of giving durability and flexibility to the roofing sheet and improving the efficiency of work such as construction and fusing property, high rigidity, high heat resistance with excellent durability, heat resistance, resin strength, and dimensional stability It is desirable to be a mixed composition of a highly functional fluorine-containing resin and a highly elastic fluorine-containing resin that imparts flexibility and fusibility. For example, in the method of laminating a low melting point resin and a high melting point resin and sticking the low melting point resin to the fiber base fabric as an inner layer, due to insufficient heat resistance of the low melting point resin, the adhesiveness is extremely lowered at the high temperature part, Problems such as deformation of the surface film due to external force occur.

  Examples of the high-rigidity and heat-resistant fluorine-containing resin include, for example, ethylene tetrafluoride-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), ethylene-tetra Fluorinated ethylene (ETFE), ethylene-trifluoroethylene chloride (ECTFE), and the like can be used. Among these, from the viewpoint of high strength and high durability, a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer resin (hereinafter abbreviated as ternary copolymer resin) having a melting point of 150 ° C. or higher is preferable. Used. Examples of the ternary copolymer resin include “THV415G”, “THV500G”, and “THV610G” manufactured by Sumitomo 3M Limited.

  Further, as the highly elastic fluorine-containing resin, a fluororubber-based resin and a low melting point fluorine-based resin are suitable. For example, a VDF-HFP resin, a VDF-HFP-TFE resin, a VDF-TFE modified resin, a fluorine-containing resin Vinyl ether resins, TFE-Pr resins, fluorine-containing silicone resins, fluorine-containing phosphazene resins, thermoplastic types, and the like can be used. In the use of the rubber-based rubber resin, it can be used in an unvulcanized state, with a vulcanizing agent added to the unvulcanized compound, or in a compound state after vulcanization. Examples of such resins include vinylidene fluoride-tetrafluoroethylene copolymer resin, vinylidene fluoride-hexafluoroethylene copolymer resin, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride ternary copolymer, and the like. At least one polymer resin is preferably used. Among them, a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer resin having a melting point of 140 ° C. or lower is blended with a high-rigidity, high-heat-resistant fluorine-containing resin, and has excellent fusion properties and flexibility. Are preferably used.

  When using a mixture of a highly rigid and high heat resistant fluorine-containing resin and a highly elastic fluorine-containing resin, the composition ratio of the highly rigid and highly heat-resistant fluorine-containing resin is 50 to 95% by weight, and the composition ratio of the highly elastic fluorine-containing resin is Is preferably in the range of 5 to 50% by weight. When the component ratio of the highly rigid and high heat-resistant fluorine-containing resin is less than 50% by weight, the heat resistance becomes insufficient, and when it exceeds 95% by weight, the fusing property and the adhesiveness may be impaired. On the other hand, if the component ratio of the highly elastic fluorine-containing resin is 5% by weight or less, the fusing property and adhesiveness are impaired, and if it exceeds 50% by weight, the dimensional stability and heat resistance are impaired.

  In the water-resistant durable roofing sheet of the present invention, an inorganic compound can be added as long as the mechanical properties of the fluorine-containing resin layer are not impaired. Examples of inorganic compounds include calcium carbonate such as heavy calcium carbonate and precipitated calcium carbonate. Barium sulfate such as barite powder and precipitated barium sulfate. Silicate compounds such as aluminum silicate (kaolinite, calcined clay, pyrophyllite, sericite, etc.), magnesium silicate (talc), calcium silicate (wollastonite), and silicic acid (crystalline silica, fused silica), synthetic silicic acid, And as a silicate, hydrous calcium silicate, hydrous aluminum silicate, and silicic acid (anhydrous silicic acid, hydrous silicic acid) can be used preferably, for example. In order to further improve the mechanical properties of the fluorine-containing resin layer, the inorganic compound may be surface-treated with a coupling agent. As the coupling agent, it is preferable to use at least one selected from a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, and a zircoaluminum coupling agent. .

The addition amount of the inorganic compound is preferably 5 to 50 parts by weight with respect to 100 parts by weight of the terpolymer resin. If the amount is less than 5 parts by weight, the effect of increasing the amount and cost is poor, and if it exceeds 50 parts by weight, the resin strength may be lowered and may not be suitable for practical use.
Further, in the water resistant and durable roofing sheet of the present invention, it is preferable to add an ultraviolet shielding agent for the purpose of improving the weather resistance. As the ultraviolet shielding agent, metal oxides such as titanium oxide, zinc oxide, iron oxide, and cesium oxide can be preferably used. In particular, it is preferable to use rutile type titanium oxide having a high shielding ability against visible light and ultraviolet light.
The addition amount of the metal oxide is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the ternary copolymer resin. If the amount is less than 0.5 part by weight, the ultraviolet ray shielding effect may be insufficient. If the amount exceeds 10 parts by weight, the processability of the resin decreases.

  In the water-resistant durable roofing sheet of the present invention, one kind of cross-linking selected from a fluorine-containing compound, at least an isocyanate compound, and a coupling agent is impregnated and fixed between the fiber base fabric and the fluorine-containing resin layer. A first adhesive layer formed by crosslinking including an agent and a second adhesive layer formed on the first adhesive layer and crosslinked by including at least a coupling agent are formed. The first adhesive layer prevents water absorption from the product surface and sheet end face, prevents water fiber deterioration under high temperature and high humidity or in a high temperature environment in contact with moisture, and adheres to the second adhesive layer. Has the effect of increasing The second adhesive layer has an effect of firmly adhering to the glass fiber and the first adhesive layer and enhancing the adhesiveness with the fluorine-containing resin layer. Even if any of the adhesive layers is missing, it is not possible to obtain the effect of preventing the product strength from being lowered due to the desired water resistance deterioration and preventing the adhesion from being lowered between the fiber base fabric and the fluorine-containing resin layer. For example, the formation of only the first adhesive layer is inferior in adhesiveness with the fluorine-containing resin, and the formation of only the second adhesive layer cannot provide long-term water resistance durability.

A 1st contact bonding layer is formed from the binder resin and at least 1 sort (s) chosen from the isocyanate compound and coupling agent which are added as a crosslinking agent by using the fluorine-type compound which has a water-repellent effect as an essential component. The addition of only a fluorine compound cannot sufficiently prevent water absorption in a high temperature environment, and a composite layer is formed by forming a crosslinked layer comprising at least one selected from an isocyanate compound and a coupling agent and a binder resin. The effect is manifested.
Moreover, a 2nd contact bonding layer expresses the adhesiveness of glass fiber and a fluorine-containing resin layer by forming a binder resin and a crosslinked layer by using a coupling agent as an essential component.

  Fluoro-based compounds used for the first adhesive layer include fluoroacrylate-acrylate copolymer, fluoroolefin-fluoroalkyl vinyl ether-hydroxyvinyl ether copolymer, fluoroolefin-vinyl ester-hydroxyvinyl ether copolymer, fluoroolefin-vinyl. Examples include ester-hydroxyallyl ether copolymers, fluoroolefin-alkyl vinyl ether-hydroxy vinyl ether copolymers, and the like. From the viewpoint of the affinity with the binder resin and the water repellent effect, a fluoroacrylate-acrylate copolymer is preferably used. The addition amount of the fluorine-based compound is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the binder resin. If it is less than 1 part by weight, the effect of preventing water absorption may be insufficient, and if it exceeds 50 parts by weight, the adhesive strength may be reduced.

Examples of the isocyanate compound used in the first adhesive layer and the second adhesive layer include aliphatic diisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate and hydrogenated tolylene diisocyanate. Aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylene diisocyanate; isocyanurates such as tris (hexamethylene isocyanate) isocyanurate and tris (3-isocyanate methylbenzyl) isocyanurate; The end of the isocyanate group of these compounds is blocked with blocking agents such as phenols, oximes, alcohols and lactams. And the like are preferably used, and part of ethylene glycol-modified isocyanates hydrophilic monomer is added, such as isocyanate groups of said compound; blocked isocyanate. From the viewpoint of dispersibility, water resistance, and adhesiveness to the base fabric, when used in an emulsion resin solution, in particular, one of the isocyanate groups of blocked isocyanate and aliphatic isocyanate has a hydrophilic unit such as ethylene glycol. It is preferable to use a modified partially trimerized isocyanurate to which a monomer is added.
It is preferable that the addition amount of an isocyanate compound is 2-30 weight part with respect to 100 weight part of binder resin. If it is less than 2 parts by weight, the adhesive strength may be insufficient, and if it exceeds 30 parts by weight, flexibility may be impaired.

  As a coupling agent used for the first adhesive layer and the second adhesive layer, from a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, and a zircoaluminum coupling agent It is preferable to use at least one selected. Examples of the silane coupling agent include aminosilanes such as γ-aminopropyltriethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane; epoxy silanes such as γ-glycidoxypropylmethyldisilane. Ethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane; vinyl silanes such as vinyltriethoxysilane and vinyltris (β-methoxyethoxy) silane; Examples include mercaptosilanes such as γ-mercaptopropyltrimethoxysilane.

  Examples of the titanium coupling agent include alkoxy compounds such as tetraisopropoxy titanium, tetra-n-butoxy titanium, and tetrakis (2-ethylhexoxy) titanium; acylates such as tri-n-butoxy titanium stearate, and Examples include isopropoxy titanium tristearate. Examples of the zirconium coupling agent include tetrabutyl zirconate, tetra (triethanolamine) zirconate, and tetraisopropyl zirconate. Examples of the aluminum coupling agent include acetoalkoxyaluminum diisopropylate. Further, examples of the zircoaluminum-based coupling agent include tetrapropylzircoaluminate. Among these coupling agents, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3,4 epoxy) are excellent in water resistance, moisture resistance, and light resistance. It is preferable to use an epoxy silane such as (cyclohexyl) ethyltrimethoxysilane.

The addition amount of the coupling agent compound is preferably 2 to 20 parts by weight with respect to 100 parts by weight of the binder resin in both the first adhesive layer and the second adhesive layer. If it is less than 2 parts by weight, the adhesive strength and water resistance may be insufficient, and if it exceeds 20 parts by weight, the flexibility of the product may be impaired.
As the binder resin used for the first adhesive layer and the second adhesive layer, it is desirable to use a fluorine-containing resin from the viewpoint of adhesiveness. In particular, it is preferable to use an aqueous dispersion type of a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer resin. As such a resin, for example, a dispersion type “THV340C” manufactured by Sumitomo 3M Limited can be used. For the purpose of further improving the adhesiveness and flexibility, one or more of an acrylic resin and a polyurethane resin may be used in combination with the fluorine-based binder resin as necessary.

The waterproof and durable roofing sheet of the present invention comprises a fiber base fabric and a fluorine-containing resin layer laminated on at least one surface thereof, and a first adhesive layer and a second adhesive layer are interposed between the fiber base fabric and the fluorine-containing resin layer. A layer is formed. As a method for forming this adhesive layer, it can be formed on the base fabric by a method such as gravure roll coating, doctor blade coating, reverse roll coating, dip coating or the like. In particular, in forming the first adhesive layer, from the viewpoint of impregnating and fixing the adhesive layer to the fiber base fabric, it is preferably formed by a dip coating method, and the fixing heating temperature is preferably 170 ° C to 250 ° C. When the heating temperature is less than 170 ° C, the adhesiveness between the fiber base fabric and the fluorine-containing resin layer is poor, and when it exceeds 250 ° C, the flexibility of the product is lowered. The fluorine-containing resin layer is formed by laminating a film formed by a method such as a calendar molding method or an extrusion molding method using a T die on the second adhesive layer by a method such as thermocompression bonding. The thickness of the fluorine-containing resin film is preferably 0.10 mm to 1.0 mm. If the thickness is less than 0.10 mm, the durability, waterproofness, and moisture resistance of the membrane material may be insufficient. If the thickness exceeds 1.0 mm, the flexibility and flexibility of the membrane material will be insufficient, resulting in workability. Damaged. The water resistant and durable roofing sheet of the present invention preferably has a product thickness of 0.40 mm to 3.0 mm as a whole. When the product thickness is less than 0.40 mm, the durability is insufficient, and when it exceeds 3.0 mm, the flexibility, flexibility, and workability are poor. Further, it is preferred that the product weight is ^{500g / m 2 ~3000g / m 2} . If the product weight is less than 500 g / m ² , the durability is insufficient, and if it exceeds 3000 g / m ² , workability during construction deteriorates.

The present invention will be described more specifically with reference to the following examples. The measurement methods used for performance evaluation of products in each example are as follows.
(1) Water resistance (i) Tensile strength retention The strength change (tensile strength retention) of the sample after immersion in warm water under the following test conditions was measured in accordance with JIS L 1096.
<Test conditions>
Hot water test: The sample is fully immersed in hot water at 80 ° C. and left for 1 month and 6 months.
<Evaluation>
Strength change: The tensile strength change rate (tensile strength retention rate) before and after the test was evaluated.
Tensile strength retention rate = tensile strength after test / tensile strength before test × 100 (%)
(Ii) Peel strength retention rate In accordance with JIS K 6328, the peel strength change (peel strength retention rate) between the fluorine-containing resin layer and the fiber base fabric layer of the sample after immersion in warm water under the following test conditions It was measured.
<Test conditions>
Hot water test: The sample is fully immersed in hot water at 80 ° C. and left for 1 month and 6 months.
<Evaluation>
Strength change: The peel strength change rate (peel strength retention) before and after the test was evaluated.
Peel strength retention rate = Peel strength after test / Peel strength before test × 100 (%)

(2) Heat resistance In accordance with JIS L 1096, the strength change (tensile strength retention) of the sample after being left in a hot-air circulating thermostatic chamber under the following test conditions was measured.
<Test conditions>
Thermal aging test: The sample is placed in a hot air circulating thermostat at 120 ° C. and left for 1 month and 6 months.
<Evaluation>
Strength change: The tensile strength change rate (tensile strength retention rate) before and after the test was evaluated.
Tensile strength retention rate = tensile strength after test / tensile strength before test × 100 (%)
(3) Weather resistance A metal weather super accelerated weathering tester (manufactured by Dainippon Plastic Co., Ltd.) was used to measure the strength change (tensile strength retention rate) of the sample after irradiation with ultraviolet rays under the following test conditions.
<Test conditions>
UV intensity: 50 (mW / cm ² )
L time (light); temperature 60 ° C, humidity 39%, set time 4 hours D time (condensation); temperature 60 ° C, humidity 90% or more, set time 4 hours Cycle time of L time and D time 8 hours A total of 15 cycles (120 hours) was set as one unit of test conditions, and a total of 10 units (1200 hours) and 30 units (3600 hours) were irradiated.
<Evaluation>
Strength change: The tensile strength change rate (tensile strength retention rate) before and after the test was evaluated.
Tensile strength retention rate = tensile strength after test / tensile strength before test × 100 (%)

(4) Sewing property (i) Hot air welding Using a variant type hot air automatic welder (manufactured by Carl Leister), joining the samples at a hot air temperature of 600 ° C and a welding speed of 6 m / min, the degree of welding of the samples evaluated.
<Evaluation>
A: Welding is performed on the entire surface
○: Partially carbonized but almost entirely welded.
Δ: Partially welded but not suitable for practical use.
X: No welding at all.
(Ii) High frequency welding A high frequency welder (Yamamoto Vinita Co., Ltd .; YF-7000) having a frequency of 40.46 MHz and a maximum output of 7 KW equipped with a 40 mm × 300 mm mold was given an oscillation time of 4 seconds and a cooling time of 4 seconds. The degree of subsequent welding was evaluated.
<Evaluation>
(Double-circle): It welds on the whole surface.
○: Almost welded.
Δ: Partially welded but not suitable for practical use.
X: No welding at all.

Example 1
As a fiber base fabric, a fabric using glass fiber yarn (fiber thickness: G yarn, woven yarn thickness: 404.9 Tex) as warp and weft (plain weave, basis weight: 570 g / m ² , density: 21 warps / 25.4 mm, 19 wefts / 25.4 mm). This fiber base fabric was dipped in a first adhesive layer-forming resin solution having the following composition, drawn, dried and solidified to form a first adhesive layer in the fiber base fabric.
First adhesive layer Tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer resin (manufactured by Sumitomo 3M; trademark: THV-340C) 100 parts by weight Aliphatic isocyanate compound 10 parts by weight Silane coupling Agent 5 parts by weight Fluorine-based compound 20 parts by weight The obtained fiber base fabric including the first adhesive layer is dipped with a resin liquid for forming a second adhesive layer having the following composition, squeezed, dried and solidified (fixed heating temperature 220 ° C. ) To form a second adhesive layer in the fiber base fabric.
Second adhesive layer Tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer resin (manufactured by Sumitomo 3M; trademark: THV-340C) 100 parts by weight Silane coupling agent 5 parts by weight A fluorine-containing resin layer having the following composition was formed on both surfaces of the fiber base fabric including the first adhesive layer and the second adhesive layer.
Composition for fluorine-containing resin layer Tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer resin (manufactured by Sumitomo 3M, trademark: THV-415G, melting point: 158 ° C.)
100 parts by weight UV absorber (titanium oxide) 3 parts by weight Pigment (carbon black) 0.1 part by weight Lubricant (Amide) 1 part by weight A murine film having a thickness and a back surface thickness of 0.25 mm each was produced. This film was thermocompression bonded to both sides of the fiber base fabric at 180 ° C. for 2 minutes to form a fluorine-containing resin layer. A roofing sheet excellent in water resistance durability of the present invention was obtained. The composition and test results of this roofing sheet are shown in Table 1 and Table 3, respectively.

Example 2
A roofing sheet was produced and tested in the same manner as in Example 1. However, the fluorine-containing resin in the fluorine-containing resin layer was a mixed composition of a highly rigid high heat-resistant fluorine-containing resin and a highly elastic fluorine-containing resin having the following composition. The composition and test results of this roofing sheet are shown in Table 1 and Table 3, respectively.
Composition for fluorine-containing resin layer Tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer resin (Highly rigid and heat-resistant fluorine-containing resin, manufactured by Sumitomo 3M, trademark: THV-415G, melting point: 158 ° C.) 75 parts by weight Tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer resin (highly elastic fluorine-containing resin, manufactured by Sumitomo 3M Limited, trademark: THV-220G, melting point: 119 ° C.) 25 parts by weight UV absorber (titanium oxide) 3 parts by weight Pigment (carbon black) 0.1 part by weight Lubricant (amide) 1 part by weight

Example 3
A roofing sheet was prepared and tested in the same manner as in Example 2. However, the first adhesive layer had the following composition. The composition and test results of this roofing sheet are shown in Table 1 and Table 3, respectively.
First adhesive layer Tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer (manufactured by Sumitomo 3M; trademark: THV-340C) 100 parts by weight Aliphatic isocyanate compound 10 parts by weight Fluorine compound 20 Parts by weight

Example 4
A roofing sheet was prepared and tested in the same manner as in Example 2. However, the first adhesive layer had the following composition. The composition and test results of this roofing sheet are shown in Table 1 and Table 3, respectively.
First adhesive layer Tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer (manufactured by Sumitomo 3M; trademark: THV-340C) 100 parts by weight Silane coupling agent 5 parts by weight Fluorine compound 20 Parts by weight

Example 5
A roofing sheet was prepared and tested in the same manner as in Example 2. However, a fabric using a polyester fiber yarn (fiber thickness: 1100 dtex, yarn thickness: 4400 dtex) as a warp and weft as a fiber base fabric (plain weave, basis weight: 580 g / m ² , density: 13 warps / 25.4 mm) , 14 wefts / 25.4 mm). The composition and test results of this roofing sheet are shown in Table 1 and Table 3, respectively.

Example 6
A roofing sheet was prepared and tested in the same manner as in Example 2. However, the fixing heating temperature when forming the second adhesive layer was set to 185 ° C. and solidified. The composition and test results of this roofing sheet are shown in Table 1 and Table 3, respectively.

Example 7
A roofing sheet was prepared and tested in the same manner as in Example 2. However, the fluorine-containing resin layer containing the fluorine-containing resin had the following composition. The composition and test results of this roofing sheet are shown in Table 1 and Table 3, respectively.
Composition for fluorine-containing resin layer Tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer resin (Highly rigid and heat-resistant fluorine-containing resin, manufactured by Sumitomo 3M, trademark: THV-415G, melting point: 158 ° C.) 75 parts by weight Tetrafluoroethylene-vinylidene fluoride copolymer (highly elastic fluorine-containing resin, manufactured by Elf Atchem Co., Ltd., trademark: KYNAR # 7200, melting point: 124 ° C.) 25 parts by weight UV absorber ( Titanium oxide) 3 parts by weight Pigment (carbon black) 0.1 part by weight Lubricant (amide) 1 part by weight

Example 8
A roofing sheet was prepared and tested in the same manner as in Example 2. However, the fluorine-containing resin layer containing the fluorine-containing resin had the following composition. The composition and test results of this roofing sheet are shown in Table 1 and Table 3, respectively.
Composition for fluorine-containing resin layer Tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer resin (Highly rigid and heat-resistant fluorine-containing resin, manufactured by Sumitomo 3M, trademark: THV-415G, melting point: 158 ° C.) 75 parts by weight propylene hexafluoride-vinylidene fluoride copolymer (highly elastic fluorine-containing resin, manufactured by Elf Atchem Co., Ltd., trademark: KYNAR # 2750, melting point: 132 ° C.) 25 parts by weight UV absorber ( Titanium oxide) 3 parts by weight Pigment (carbon black) 0.1 part by weight Lubricant (amide) 1 part by weight

Comparative Example 1
A roofing sheet was produced and tested in the same manner as in Example 1. However, the fluorine-type compound of the 1st contact bonding layer was removed. The composition and test results of this roofing sheet are shown in Table 2 and Table 3, respectively.
Comparative Example 2
A roofing sheet was produced and tested in the same manner as in Example 1. However, the first adhesive layer was not formed. The composition and test results of this roofing sheet are shown in Table 2 and Table 3, respectively.
Comparative Example 3
A roofing sheet was produced and tested in the same manner as in Example 1. However, the silane coupling agent of the second adhesive layer was removed. The composition and test results of this roofing sheet are shown in Table 2 and Table 3, respectively.
Comparative Example 4
A roofing sheet was produced and tested in the same manner as in Example 1. However, the second adhesive layer was not formed. The composition and test results of this roofing sheet are shown in Table 2 and Table 3, respectively.

Comparative Example 5
As a base fabric, a fabric (plain weave, basis weight: 500 g / m ²⁾ , density: 24 warps / 25 using glass fiber yarn (fiber thickness: cocoon yarn, woven yarn thickness: 540.0 Tex) as warp and weft 4 mm, 19 wefts / 25.4 mm). This base fabric was immersed in an aqueous dispersion of tetrafluoroethylene resin by an impregnation method, and was repeatedly dipped, dried and fired to produce a waterproof sheet having a thickness of 0.80 mm and a mass of 1.3 kg / m ² . The composition and test results of this waterproof sheet are shown in Table 2 and Table 3, respectively.

Comparative Example 6
A waterproof sheet was produced and tested in the same manner as in Example 1. However, a vinyl chloride resin composition having the following composition was used as the resin for the waterproof coating layer. The composition and test results of this waterproof sheet are shown in Table 2 and Table 3, respectively.
Vinyl chloride resin composition Vinyl chloride resin 100 parts by weight Phthalate ester plasticizer 50 parts by weight Phosphate ester plasticizer 15 parts by weight Epoxy compound 3 parts by weight Ba-Zn stabilizer 1 part by weight Processing aid 3 parts by weight Benzo 0.1 parts by weight of triazole ultraviolet absorber

Comparative Example 7
A plain woven glass fiber cloth (E glass, basis weight 460 g / m ² , aminosilane coupling treatment) was used as the base fabric. This base fabric was impregnated with a dispersion of tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer, and further, a high melting point tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer film. And a low-melting ethylene tetrafluoride-hexafluoropropylene-vinylidene fluoride copolymer film, heat-sealed and pressure-bonded with the lower melting point in contact with the glass fiber cloth, Produced. The composition and test results of this waterproof sheet are shown in Table 2 and Table 3, respectively.

  Excellent flexibility and sewability during construction, and excellent product strength retention and adhesive retention even in high temperature and high humidity environments, especially in high temperature environments where it comes into contact with moisture. This is useful for roofing waterproof sheets.

Cross-sectional explanatory drawing which shows the structure of an example of the water-resistant durability roofing sheet of this invention. Cross-sectional explanatory drawing which shows the structure of the other example of the waterproofing durability roofing sheet of this invention. Cross-sectional explanatory drawing which shows the structure of the further another example of the water-resistant durability roofing sheet | seat of this invention. Cross-sectional explanatory drawing which shows the structure of the further another example of the water-resistant durability roofing sheet | seat of this invention.

Explanation of symbols

1-1. Glass fiber base cloth 1-2. Polyester fiber base cloth 2. Cross-linked first adhesive layer 3 containing a fluorine-containing compound, an isocyanate compound and a coupling agent. 2 Adhesive layer 4-1 Fluorine-containing resin layer 4-2 Fluorine-containing resin layer 4-3 made of a mixed composition of a highly rigid and high heat-resistant fluorine-containing resin and a highly elastic fluorine-containing resin. Fluorine-Containing Resin Layer Made of Propylene Propylene-Vinylidene Fluoride Terpolymer

Claims (7)

In a laminate comprising a fiber base fabric and a fluorine-containing resin layer formed on at least one surface thereof, between the fiber base fabric and the fluorine-containing resin layer,
A first adhesive layer that is impregnated and fixed to a fiber base fabric and includes a fluorine-containing compound and at least one cross-linking agent selected from an isocyanate compound and a coupling agent, and is formed by cross-linking;
A second adhesive layer formed on the first adhesive layer and including a coupling agent and formed by crosslinking;
A roofing sheet excellent in water resistance and durability.   The fluorine-containing resin layer is composed of at least two monomers selected from at least vinylidene fluoride, ethylene trifluoride, ethylene trifluoride chloride, ethylene tetrafluoride, hexafluoropropylene, fluoroalkyl vinyl ether, and ethylene. The roofing sheet excellent in water resistance durability of Claim 1 containing at least 1 sort (s) of the fluorine-type copolymer resin which becomes.   The water resistance according to claim 1 or 2, wherein the fluorine-containing resin layer contains a mixed composition of 50 to 95% by mass of a highly rigid and highly heat-resistant fluorine-containing resin and 5 to 50% by mass of a highly elastic fluorine-containing resin. Durable roofing sheet.   The high-rigidity and heat-resistant fluorine-containing resin of the fluorine-containing resin contains a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer resin and has a melting point of 150 ° C or higher. The roofing sheet with excellent water resistance and durability described in 1.   The highly elastic fluorine-containing resin of the fluorine-containing resin layer is a vinylidene fluoride-tetrafluoroethylene copolymer resin, a vinylidene fluoride-hexafluoroethylene copolymer resin, a tetrafluoroethylene-hexafluoropropylene-fluoride. The roofing sheet excellent in water resistance durability according to claim 3, comprising at least one selected from vinylidene chloride terpolymer resins.   The highly elastic fluorine-containing resin of the fluorine-containing resin layer contains a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer resin and has a melting point of 140 ° C. or lower. Roofing sheet with excellent water resistance.   The first adhesive layer and the second adhesive layer each contain a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer resin as a binder, respectively. Roofing sheet with excellent water resistance.

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