JP6912263B2 - Laminated sheet - Google Patents

Description

The present invention relates to a laminated sheet that can be used as a waterproof sheet (for example, under-roofing material) for covering a base of a building or a structure.

Traditionally, roofs in Japanese houses usually have a structure in which asphalt roofing is interposed as a roofing material for the purpose of waterproofing between a roof base material such as plywood or field board and a roof material such as roof tiles. There is. As the asphalt roofing used for this under-roofing material, asphalt roofing 940 specified in JIS A 6005 asphalt roofing felt is widely used. In particular, this asphalt roofing 940 is used for secondary waterproofing of a gradient roof, but has a unit area mass of 0.94 kg / m ² or more, and 19.7 kg for a roll body distributed in a roll of 21 m. It becomes the above heavy object. Further, many of the under-roofing materials using modified asphalt have the same composition, and no under-roofing material using asphalt with a weight of 15 kg or less can be found. In recent years, Japan is facing an aging society as the population declines, and the working age of workers at construction sites is also rising. Therefore, it has been pointed out that there is a danger of working with heavy objects at the construction site of under-roofing materials that are required to work at high places, and lighter asphalt roofing is required.

On the other hand, Japanese Patent Application Laid-Open No. 2012-167451 (Patent Document 1) describes polyester filaments containing a two-component additive-type liquid silicone rubber and an inorganic filler as a lightweight and workable under-roofing material. The surface layer formed of the non-woven fabric, the intermediate layer formed of the polyester ultrafine fiber non-woven fabric obtained by the melt blow method, and the back surface layer formed of the polyester long-fiber non-woven fabric containing modified asphalt are integrated by thermal pressure bonding. The under-roofing material made of the laminated non-woven fabric is disclosed.

However, although this under-roofing material is lightweight, it has a complicated layer structure, low productivity, insufficient waterproofness, and, for example, low sealing performance when nailed.

On the other hand, Japanese Patent Application Laid-Open No. 2013-160468 (Patent Document 2) describes a waterproof layer having a water pressure resistance of 4 kPa or more formed of a polyethylene resin film and / or asphalt-impregnated paper as a waterproof sheet having excellent nail hole sealing properties. A waterproof sheet having a grain size of 120 to 300 g / m ² on at least one surface and having a plurality of embossed recesses formed at intervals in the vertical and horizontal directions is laminated on the surface on the waterproof layer side is disclosed. .. This document describes that the waterproof layer is preferably formed of a polyethylene-based resin film alone from the viewpoints of transparency, light weight, bendability, and the like. In the examples of this document, a polyethylene airtight film, a polyethylene breathable film, or asphalt felt is used as the waterproof layer.

However, since the polyethylene-based resin film and the asphalt-impregnated paper having low fluidity do not have sufficient nail hole sealing property, the thickness of the hydrophobic layer becomes large in order to improve the nail hole sealing property.

Japanese Unexamined Patent Publication No. 2012-167451 (Claims, Examples) Japanese Unexamined Patent Publication No. 2013-100648 (Claims, Examples)

Therefore, an object of the present invention is to provide a laminated sheet that is lightweight but highly waterproof.

Another object of the present invention is to provide a laminated sheet having a high nail hole sealing property even if it has a thin thickness and a simple structure.

Still another object of the present invention is to provide a laminated sheet which can suppress exudation of asphalt, has excellent handleability, and can prevent blocking even when stored and transported in a rolled state.

As a result of diligent studies to achieve the above problems, the present inventors have made waterproof even if it is lightweight by interposing a non-porous intermediate layer between the waterproof layer containing asphalt and the fiber layer. The present invention has been completed by finding that a laminated sheet having high properties can be obtained.

The laminated sheet of the present invention is composed of a waterproof layer containing asphalt, an intermediate layer laminated on at least one surface of the waterproof layer and non-porous, and a fiber structure laminated on the intermediate layer. Includes a fiber layer. The fiber structure may be a hydrophobic non-woven fabric having a plurality of embossed recesses on the waterproof layer side (particularly, a polypropylene-based long fiber non-woven fabric). The intermediate layer may contain a polyolefin resin. The average thickness of the waterproof layer may be 500 μm or less. The waterproof layer may be a structure that does not include a fiber structure. The unit area mass of the laminated sheet of the present invention ^{may be 0.9 kg / m 2} or less. In the laminated sheet of the present invention, an intermediate layer and a fiber layer may be laminated on both sides of the waterproof layer, respectively. The laminated sheet of the present invention may be a waterproof sheet (particularly, under-roofing material) for covering the base of a building or a structure.

In the present specification and claims, the "fiber structure" means a sheet-shaped molded body (or fabric) formed by an aggregate of fibers, and the "embossed recess" means the formation of a recess. Regardless of whether the method is embossed or not, it means a recess in which at least a part of the bottom portion (bottom wall) and the side portion (side wall) forming the recess is formed by the fused portion of the fiber. ..

In the present invention, since the non-porous intermediate layer is interposed between the waterproof layer containing asphalt and the fiber layer, the waterproof property can be improved even if the weight is light. Further, even if the thickness is thin and the structure is simple, the nail hole sealing property can be improved. Furthermore, since asphalt exudation can be suppressed, it is easy to handle, and by forming fiber layers on both sides of the waterproof layer via intermediate layers, blocking can be prevented even when stored and transported in a rolled state. ..

FIG. 1 shows a scanning electron micrograph of the embossed recess of the laminated sheet obtained in Example 3. FIG. 2 shows a scanning electron micrograph of the embossed recess of the laminated sheet obtained in Comparative Example 4.

[Laminated sheet]
The laminated sheet of the present invention is composed of a waterproof layer containing asphalt, an intermediate layer laminated on at least one surface of the waterproof layer and non-porous, and a fiber structure laminated on the intermediate layer. Includes a fiber layer. In the present invention, since the intermediate layer is interposed between the waterproof layer and the fiber layer, it is possible to prevent the asphalt of the waterproof layer from impregnating the fiber layer. Therefore, the thickness of the waterproof layer can be uniformly maintained, and even if the thickness of the waterproof layer is thin and lightweight, the waterproof property and the nail hole sealing property can be improved.

(Waterproof layer)
The waterproof layer contains asphalt as the main component. Examples of asphalt include natural asphalt (lake asphalt, rock asphalt, oil sand, asphalt tight, etc.), petroleum asphalt (straight asphalt, blown asphalt, etc.) and the like. These asphalts can be used alone or in combination of two or more. Of these, petroleum asphalt such as straight asphalt is widely used.

The degree of needle insertion (1/10 mm) of asphalt can be selected from the range of about 0 to 300 in a method based on JIS K2207-1996, for example, about 5 to 200, preferably about 10 to 150, and more preferably about 20 to 100. Is. If the degree of needle insertion is too small, it may be difficult to form a uniform thin film, and if it is too large, the adhesiveness to the intermediate layer may be lowered and the nail hole sealing property may be lowered.

The asphalt may be used as a modified asphalt by combining with a modifier. The modifier includes an organic modifier and an inorganic modifier.

Examples of the organic modifier include polyolefins and vinyl polymers (polyvinyl chloride, polyvinyl acetate, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, ethylene-acrylic acid copolymers, ethylene). -Methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, etc.), polyamide, polyester, synthetic rubber or elastomer (polybutadiene, polyisoprene, styrene-butadiene copolymer, etc.), natural rubber, rosin-based resin (natural) (Rodin, modified rosin, etc.) and the like. These organic modifiers can be used alone or in combination of two or more. Among these organic modifiers, thermoplastic elastomers, particularly styrene-diene copolymers such as styrene-butadiene-styrene block copolymers, are preferable.

Examples of the inorganic modifier include metal particles (powder) such as iron, copper, tin, zinc, nickel, and stainless steel; iron oxide, iron sesquioxide, iron tetraoxide, ferrite, tin oxide, zinc oxide, etc. Metal oxide particles such as zinc flower, copper oxide, aluminum oxide; metal salt particles such as barium sulfate, calcium sulfate, aluminum sulfate, calcium sulfite, calcium carbonate, calcium bicarbonate, barium carbonate, magnesium hydroxide; steelmaking slag, mica , Clay, talc, wollastonite, diatomaceous soil, silica sand, mineral particles such as pebble powder; inorganic fibers such as glass fiber and carbon fiber. These inorganic modifiers can be used alone or in combination of two or more. Among these inorganic modifiers, particulate modifiers such as iron particles, various iron oxide particles, steelmaking slag particles, and (heavy) calcium carbonate particles are preferable. The average particle size of the particulate modifier is about 0.01 to 0.5 mm (particularly 0.05 to 0.2 mm).

The organic modifier and the inorganic modifier may be used in combination in order to improve the adhesiveness and the light-shielding property. In the present invention, it is preferable to include at least an organic modifier from the viewpoint of improving the adhesiveness to the intermediate layer.

The ratio of asphalt to the modifier can be selected from the range of, for example, asphalt / modifier = 100/0 to 30/70, for example, 99/1 to 40/60, preferably 98/2 to 50 /. It can be selected from the range of 50, more preferably 95/5 to 60/40. When the modifier is an organic modifier, the ratio of the two is, for example, asphalt / organic modifier = 100/0 to 70/30, preferably 99/1 to 80/20, and more preferably 95. It is about / 5 to 85/15. If the proportion of the modifier is too small, the modifying effect will not be exhibited, and if it is too large, the viscosity will increase, making processing difficult, and there is a risk that economic efficiency will decrease.

The tarpaulin may contain other components, for example, conventional additives and fibers, as long as the characteristics of the main component asphalt (or modified asphalt) are not impaired, but the waterproof layer may contain conventional additives and fibers, such as under-roofing materials. It is preferable not to contain fibers (particularly fiber structures) contained in a general-purpose waterproof sheet. In the present invention, the asphalt of the waterproof layer can be fixed by the intermediate layer even if the fiber structure is not included, and the exudation of the asphalt to the surface can be suppressed.

The proportion of asphalt (or modified asphalt) in the waterproof layer may be 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass, and 100% by mass (asphalt only). May be good.

In the present invention, since the intermediate layer is interposed between the waterproof layer and the fiber layer, the waterproof layer is not affected by the shape of the fiber layer and can maintain a uniform thickness, so that it is waterproof even if it is thin. Can be maintained. The average thickness of the waterproof layer may be 1 mm or less (particularly 500 μm or less), but is, for example, 50 to 500 μm, preferably 100 to 450 μm (for example, 150 to 400 μm), and more preferably 200 to 350 μm (particularly 250 to 320 μm). It may be. If the average thickness of the waterproof layer is too large, the lightness may decrease.

(Middle layer)
The intermediate layer can suppress the asphalt of the waterproof layer from impregnating the fiber layer, can maintain the thickness of the waterproof layer uniformly, and can also suppress the asphalt from seeping out to the surface.

The intermediate layer may be non-porous so that the asphalt of the waterproof layer can prevent invasion. Therefore, the material of the intermediate layer is not particularly limited, but it is preferable to contain a resin from the viewpoint of light weight and handleability.

The resin may be, for example, a thermoplastic resin or a thermosetting resin, but a thermoplastic resin is preferable from the viewpoint of moldability and flexibility.

Examples of the thermoplastic resin include polyolefin resins (polyethylene resins, polypropylene resins, etc.), styrene resins (polystyrene, styrene-acrylonitrile copolymers, etc.), fluororesins (polytetrafluoroethylene, etc.), (meth). Examples thereof include acrylic resins (polymethyl methacrylate, etc.). These thermoplastic resins can be used alone or in combination of two or more. Among these thermoplastic resins, a polyolefin resin (for example, a polyethylene resin such as polyethylene or a polypropylene resin such as polypropylene) is preferable from the viewpoint of flexibility and waterproofness, and from the viewpoint of light weight and workability. , Polyethylene resin is particularly preferable.

The polyethylene-based resin may be an ethylene homopolymer or an ethylene-based copolymer. Examples of the copolymerizable monomer include α-olefins other than ethylene [for example, propylene, 1-butane, 1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1- _{Α-C 3-10} olefins such as heptene and 1-octene (particularly α-C _3-6 olefins)], (meth) acrylic monomers [for example, methyl (meth) acrylate and (meth) acrylic (Meta) acrylates such as ethyl acid C _1-6 alkyl esters], unsaturated carboxylic acids (eg, maleic anhydride), vinyl esters (eg, vinyl acetate, vinyl propionate, etc.), dienes (butadiene, etc.) , Isoprene, etc.) can be exemplified. These copolymerizable monomers may be used alone or in combination of two or more. Among these copolymerizable monomers, α-olefins such as propylene and vinyl esters such as vinyl acetate are preferable.

In the ethylene-based copolymer, the ratio (molar ratio) of ethylene to the copolymerizable monomer (for example, α-olefin other than ethylene) is the former / the latter = 50/50 to 99.9 / 0.1, It is preferably about 60/40 to 99.5 / 0.5, and more preferably about 70/30 to 99/1.

Polyethylene-based resins include, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear polyethylene (for example, linear low-density polyethylene), branched chain polyethylene, ionomer, chlorinated polyethylene, and ethylene-vinyl acetate. It may be a copolymer or the like.

The intermediate layer may contain additives. Additives include, for example, stabilizers (light-resistant stabilizers, heat-resistant stabilizers, etc.), colorants, fillers, plasticizers, lubricants, thickeners, leveling agents, defoamers, flame retardants, antistatic agents, and surfactants. Examples thereof include activators, dispersants, insect repellents (antistatic agents, etc.), preservatives (antifungal agents, etc.), and the like. These additives can be used alone or in combination of two or more. The ratio of the additive is 50% by mass or less, preferably 0.01 to 30% by mass, and more preferably about 0.1 to 10% by mass with respect to the entire intermediate layer.

The intermediate layer is usually a resin sheet or a resin film. The proportion of the resin in the intermediate layer may be 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and 100% by mass (resin only).

Since the intermediate layer is non-porous, it is preferably a layer having low air permeability and having no pores having a pore diameter of 20 μm or more (preferably 15 μm or more, more preferably 10 μm or more, particularly 5 μm or more), and is substantially substantially. It may be a layer having no holes in the surface, and may be a layer that does not allow air to pass through, for example, in the method for measuring ISO air permeability based on ISO5636-5.

The average thickness of the intermediate layer may be 5 μm or more, for example, 5 to 100 μm, preferably 10 to 50 μm, and more preferably 12 to 30 μm (particularly 15 to 25 μm). If the thickness of the intermediate layer is too thin, the asphalt may impregnate the fiber layer.

(Fiber layer)
The fiber layer is formed of a fiber structure, and by covering the surface of the waterproof layer via the intermediate layer, the waterproofness and mechanical strength of the laminated sheet can be improved, and asphalt of the waterproof layer also exudes. It can be suppressed and the handleability of the laminated sheet can be improved.

Examples of fibers constituting the fiber structure include natural fibers (cellulose fibers such as cotton and hemp), regenerated fibers (rayon, etc.), semi-synthetic fibers (cellulose ester fibers, etc.), and synthetic fibers [polyolefin fibers (polyethylene). Polyfibers such as fiber, polypropylene fiber, styrene fiber, polytetrafluoroethylene fiber, acrylic fiber, vinyl alcohol fiber (ethylene vinyl alcohol fiber, etc.), polyester fiber (polyethylene terephthalate, polyethylene naphthalate, etc.) C _2-4 alkylene allylate fiber, total aromatic polyester fiber such as liquid crystal polyester fiber), polyamide fiber (aliphatic polyamide fiber such as polyamide 6 and polyamide 66, total aromatic polyamide fiber such as aramid fiber) Etc.), polyurethane fibers, etc.], inorganic fibers (carbon fibers, glass fibers, etc.), etc. can be exemplified. The synthetic fiber may be a composite fiber in which different kinds of resin components are combined. These fibers can be used alone or in combination of two or more. Among these fibers, synthetic fibers such as polyolefin fibers and polyester fibers and inorganic fibers are widely used, but fibers having a hydrophobic surface are preferable from the viewpoint of waterproofness.

Fibers having a hydrophobic surface are made of water-repellent hydrophilic fibers (such as water-repellent polyethylene terephthalate fibers), a sheath made of a hydrophobic resin, and a core made of a hydrophilic resin. Although it may be a core-sheath type composite fiber or the like, a hydrophobic fiber is widely used from the viewpoint of durability and the like.

Examples of hydrophobic fibers include polyolefin fibers (polyethylene fibers, polypropylene fibers, etc.), styrene fibers (polystyrene fibers, styrene-acrylonitrile copolymer fibers, etc.), and fluororesin fibers (tetrafluoroethylene fibers, etc.). , Organic fibers such as (meth) acrylic fibers; inorganic fibers such as carbon fibers and glass fibers. These hydrophobic fibers can be used alone or in combination of two or more. Among these hydrophobic fibers, polyolefin fibers (for example, polyethylene fibers such as polyethylene fibers and polypropylene fibers such as polypropylene fibers) are preferable from the viewpoint of flexibility and water resistance, and have heat resistance and critical properties. Polypropylene fibers are particularly preferable because of their excellent points.

The polypropylene-based resin constituting the polypropylene-based fiber may be a propylene homopolymer or a propylene-based copolymer. Examples of the copolymerizable monomer include α-olefins other than propylene [for example, ethylene, 1-butene, 1-pentene, 1-hexene, 3-methylpentene, 4-methylpentene, 4-methyl-1-butene. , 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene and other α-C _2-16 olefins (particularly α-C _2-6 olefins such as ethylene and butene)] Etc. can be exemplified. These copolymerizable monomers can be used alone or in combination of two or more.

In the propylene-based copolymer, the ratio (molar ratio) of propylene to the copolymerizable monomer (for example, α-olefin such as ethylene) is the former / the latter = 70/30 to 99.9 / 0.1, It may be preferably about 80/20 to 99.5 / 0.5, and more preferably about 90/10 to 99/1.

Further, the polypropylene-based resin may be a crystalline polypropylene-based resin or a non-crystalline polypropylene-based resin.

Examples of the polypropylene-based resin include a propylene homopolymer, a propylene-ethylene random copolymer, a propylene-butene random copolymer, and a propylene-ethylene-butene random ternary copolymer.

These polypropylene-based resins can be used alone or in combination of two or more. Of these, crystalline polypropylene-based resins, particularly polypropylene homopolymers (crystalline polypropylene homopolymers), are preferable from the viewpoint of rigidity and heat resistance.

The polypropylene-based resin may be an atactic polymer, or may have a structure having three-dimensional regularity such as an isotactic, a syndiotactic, or a polypropylene-based resin obtained by using a metallocene catalyst. Of these, polypropylene-based resins having an isotactic structure are preferable from the viewpoints of crystallinity and convenience.

The fiber structure may also contain additives inside the fiber or on the surface of the fiber. As the additive, the additive exemplified in the section of the intermediate layer can be used. The ratio of the additive is 50% by mass or less, preferably 0.01 to 30% by mass, and more preferably 0.1 to 10% by mass with respect to the entire fiber structure.

Fiber structures include woven fabrics, knitted fabrics, non-woven fabrics, nets, paper and the like. The fiber structure may be a composite (laminated body) of these. Of these, a non-woven fabric is preferable from the viewpoint of mechanical properties and the like.

The average fineness of the fibers constituting the fiber structure is about 0.1 denier or more, for example, 0.1 to 5 denier, preferably 0.2 to 4 denier, and more preferably about 0.5 to 3 denier. May be good. If the fineness is too small, the effect of improving mechanical properties may be reduced.

The average fiber length is preferably long fibers, preferably more than 150 mm, for example, 200 mm or more, preferably 500 mm or more, more preferably 1000 mm or more, and is infinite length, from the viewpoint of improving mechanical properties such as strength. You may. The long-fiber non-woven fabric can be produced by a conventional method, for example, a direct spinning method such as a spunbond method, a melt blow method, or a flash spinning method. Of these, the non-woven fabric obtained by the spunbond method is widely used from the viewpoint of economy and the like.

Basis weight of the fiber structure may be a 10 g / ^{m 2} or more (e.g., 10 to 500 g / ^{m 2} or so), for example 10 to 300 g / ^{m 2,} preferably 30 to 200 g / ^{m 2,} more preferably 50~150g It is about / m ² (particularly 60 to 80 g / m ^2). If the basis weight is too small, the effect of improving mechanical properties such as strength may decrease.

The fiber structure (particularly, a non-woven fabric such as a long-fiber non-woven fabric) can be prepared through a conventional method, for example, a step of forming a web containing the fiber and a step of adhering the web, and specifically, a spunbond method. It can be prepared by the melt blow method, flash spinning method, chemical bond method, thermal bond method, thermal embossing method, spunlace method, needle punch method, stitch bond method and the like. Of these, the thermal embossing method is preferable from the viewpoint of simplicity and the like.

The fiber structure may have an embossed recess formed by the thermal embossing method or the like. In a fiber structure having embossed recesses, the thickness of the waterproof layer tends to be uneven due to deformation of asphalt and impregnation into the fiber layer, and this tendency is particularly likely to occur in a fiber structure having a plurality of embossed recesses on the waterproof layer side. Since it is large, the effect of the present invention is large.

The plurality of embossed recesses may be regularly arranged at intervals on the surface of the fiber structure (fiber layer), for example, may be arranged at equal intervals in the vertical and horizontal directions, and at equal intervals. They may be arranged in a staggered manner. Further, the embossed recesses are preferably formed at least on the waterproof layer side, and may be formed on both sides (waterproof layer side and surface side).

The planar shape of the embossed recess is not particularly limited, and examples thereof include a polygon, a circle, and an ellipse. The embossing diameter (average diameter) of the embossed recess may be, for example, 10 to 3000 μm, preferably 20 to 2500 μm, and more preferably about 50 to 2000 μm. Area of the bottom of the embossed depression (or the area of the opening) is, for example 5 × ¹⁰ -4 ~5mm ^2, preferably may be 1 × ¹⁰ -3 ~4mm ² about. The depth of the embossed recess may be less than the thickness of the fiber layer, and is, for example, 0.1 to 0.9 times, preferably 0.2 to 0.8 times, more preferably 0 times the thickness of the fiber layer. It may be about 3 to 0.7 times. The embossed area ratio of the fiber layer may be, for example, 5 to 50%, preferably about 10 to 40%.

The average thickness of the fiber layer (average thickness of the region other than the embossed recess) may be 100 μm or more, for example, 100 to 1000 μm, preferably 150 to 800 μm, and more preferably 200 to 500 μm (particularly 250 to 350 μm). You may. If the fiber layer is too thin, the mechanical properties of the laminated sheet may deteriorate.

(Characteristics of laminated sheet)
In the laminated sheet of the present invention, the fiber layer may be laminated on at least one surface of the waterproof layer with the intermediate layer interposed therebetween, but from the viewpoint of excellent handleability and prevention of blocking in the roll body. It is preferable to laminate the fiber layer on both sides of the waterproof layer via the intermediate layer. When the intermediate layer and the fiber layer are laminated on both sides, the two intermediate layers and the fiber layer may be different or the same, but they are usually the same from the viewpoint of productivity and the like.

An adhesive layer (or adhesive layer) may be further interposed between the layers of the laminated sheet of the present invention. The adhesive layer includes conventional adhesives and adhesives, for example, olefin adhesives or adhesives, (meth) acrylic adhesives or adhesives, polyester adhesives or adhesives, urethane adhesives or adhesives, It may be an adhesive layer formed of an epoxy-based adhesive, an asphalt-based adhesive, a rubber-based adhesive, or the like. The adhesive layer is preferably interposed between the intermediate layer and the fiber layer.

The average thickness of the adhesive layer may be, for example, 2 to 60 μm, preferably 4 to 30 μm, and more preferably 10 to 20 μm.

The laminated sheet of the present invention has high waterproofness (water resistance), and in a method based on the water resistance test of JIS L1092, the water pressure resistance may be 1 kPa or more, for example, 5 to 200 kPa, preferably 10 to 150 kPa. More preferably, it is about 15 to 100 kPa.

The laminated sheet of the present invention is lightweight and may have a mass per unit area (unit area mass) of 0.9 kg / m ² or less (particularly 0.8 kg / m ² or less), for example, 0.2 to 0.2 to 0.8 kg / ^{m 2,} preferably 0.3~0.7kg / ^{m 2} (e.g. 0.35~0.65kg ^{/ m} 2), more preferably 0.4~0.6kg / ^{m 2} (particularly 0. It is about 45 to 0.55 kg / m ^2).

The laminated sheet of the present invention is thin, for example, about 0.3 to 3 mm, preferably 0.5 to 2 mm, and more preferably about 0.6 to 1.5 mm (particularly 0.8 to 1.2 mm).

[Manufacturing method of laminated sheet]
The laminated sheet of the present invention only needs to be able to bond and integrate each layer, and a conventional bonding method can be used. However, since the asphalt of the waterproof layer has hot melt adhesiveness, the waterproof layer and the intermediate layer can be used. As a method of adhering the above, for example, a thermal laminating method is preferably used. In the thermal laminating method, any method may be used as long as the asphalt of the waterproof layer is in contact with the intermediate layer and solidified in a heat-fused state, and both layers are thermally laminated with the intermediate layer before the asphalt is cooled and solidified. Can be integrated. Specifically, heat-melted asphalt may be applied onto the intermediate layer and then cooled to solidify.

The heating temperature for heating and melting the asphalt is, for example, 80 to 250 ° C., preferably 150 to 240 ° C., and more preferably 180 to 200 ° C.

Examples of the asphalt coating method include conventional coating methods, such as a bar coating method, a spin coating method, a comma coating method, a die coating method, and a spray coating method.

When the intermediate layers (intermediate layer and fiber layer) are laminated on both sides of the waterproof layer, the asphalt applied on the first intermediate layer is placed on the asphalt before the asphalt is cooled and solidified. The layers may be further laminated. After laminating, it may be cooled and solidified, but usually, a laminated sheet is obtained by leaving it to solidify.

The method of adhering the intermediate layer and the fiber layer is not particularly limited, and the fiber layer may be adhered to the intermediate layer in which the waterproof layer is laminated. However, since the intermediate layer is thin, the intermediate layer and the fiber layer are bonded in advance. After the integration, the method of integrating with the waterproof layer by the above-mentioned thermal laminating method is preferable. Examples of the bonding method between the intermediate layer and the fiber layer include a conventional method, an bonding method in which both layers are bonded via the bonding layer, and a thermal laminating method in which the fiber layer and the intermediate layer in a molten state are thermally laminated. As a method of adhering the intermediate layer and the fiber layer, a heat laminating method is preferable. In addition, a commercially available product in which the intermediate layer and the fiber layer are integrated can also be used.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. The materials used in the examples and the method for measuring each physical property value in the examples are shown below.

[Material used]
Polypropylene (PP) long fiber non-woven fabric-polyethylene (PE) film laminate A: PP long fiber non-woven fabric (PT. Multi Spunindo JAYA "Product No. PRPW070") with a grain size of ^{70 g / m 2 with polyethylene having a thickness of 20 μm.} Heat-laminated laminate PP long-fiber non-woven fabric B: PP long-fiber non-woven fabric with a grain of ^{70 g / m 2 (PT. Multi Spunindo JAYA "Product No. PRPW070")}
Polyester long fiber non-woven fabric-ethylene-vinyl acetate copolymer (EVA) film laminate C: "Spunbond HD Lami" manufactured by Yasuhara Chemical Co., Ltd., a polyester long fiber non-woven fabric with a ^{grain size of 30 g / m 2 and an EVA film with a thickness of 20 μm} Laminated modified asphalt: A mixture of 93 parts by mass of straight asphalt 60-80 and 7 parts by mass of styrene-butadiene-styrene block copolymer 3 types of asphalt for waterproofing work: Asphalt for waterproofing work conforming to JIS K 2207 3 types

[Nail hole sealing property]
The nail hole sealing property was evaluated according to the "7.8 Nail hole sealing property test" of the Asphalt Roofing Industry Association "Modified Asphalt Roofing Underlaying Material ARK 04s-03: 2006". Specifically, the laminated sheets obtained in Examples and Comparative Examples are placed on a water-resistant plywood (thickness 12 mm) of 100 mm × 100 mm, and a ring is placed until the nail head is about 10 mm above the laminated sheet. A test piece for ring nails that was fixed by hitting a nail (average diameter of the shaft: 3.2 mm, length of the foot: 32 mm) straight, and a staple that was fixed by hitting the staple straight until the nail head was directly above the laminated sheet. Ten staple test pieces were prepared. A polyvinyl chloride tube (inner diameter 40 mm) cut to 40 mm was placed on the laminated sheet so that the position of the nail hole was located at the center of the cut surface of the tube. The contact portion between the polyvinyl chloride pipe and the waterproof sheet was sealed with a sealing material, and the sealing material was cured to prepare a test piece. Water was injected into the polyvinyl chloride pipe of the test body (water head 30 mm), allowed to stand for 24 hours, and then the presence or absence of water leakage was confirmed. The nail hole sealing property was evaluated according to the following criteria by counting the number of test bodies in which water leakage occurred (number of water leaks) out of the 10 test bodies. The evaluation "○" is a condition in which no water leakage is observed in the ARK 04s-03: 2006 standard.

〇: 2 or less leaks Δ: 3 to 4 leaks ×: 5 or more leaks.

[Asphalt wettability]
The presence or absence of wet asphalt on the surface was visually observed and the presence or absence was evaluated.

[Water resistance]
It was measured by the A method (low water pressure method) using a high water pressure water resistance tester (“WP-1000K” manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.) in accordance with JIS L 1092.

Example 1
The PE film side of the first PP long-fiber non-woven fabric-PE film laminate A is coated with a modified asphalt melted by heating at a temperature of 160 ° C. with an average thickness of 0.1 mm using a die coater. While the modified asphalt was adherent, the PE film side of the second PP long fiber non-woven fabric-PE film laminate A was further bonded onto the coated modified asphalt to form a laminated sheet. Obtained.

Example 2
A laminated sheet was obtained in the same manner as in Example 1 except that the average thickness of the modified asphalt was changed to 0.2 mm.

Example 3
A laminated sheet was obtained in the same manner as in Example 1 except that the average thickness of the modified asphalt was changed to 0.3 mm.

Example 4
On the PE film side of the first PP long-fiber non-woven fabric-PE film laminate A, three types of asphalt for waterproofing work melted by heating at a temperature of 160 ° C. are coated with an average thickness of 0.3 mm using a die coater. While the three types of coated asphalt for waterproofing work have adhesiveness, the three types of asphalt for waterproofing work coated on the PE film side of the second PP long-fiber non-woven fabric-PE film laminate A It was laminated on top to obtain a laminated sheet.

Example 5
PP long fiber non-woven fabric-PE film The PE film side of the laminate A is coated with 3 types of asphalt for waterproofing work that has been melted by heating at a temperature of 160 ° C with an average thickness of 0.3 mm using a die coater. While the three types of asphalt for waterproofing work had adhesiveness, the EVA film side of the polyester long fiber non-woven fabric-EVA film laminate C was further bonded onto the three types of asphalt for waterproofing work. A laminated sheet was obtained. The obtained laminated sheet was subjected to various characteristics tests with the PP long fiber non-woven fabric-PE film laminate A as the upper surface.

Example 6
The laminated sheet obtained in Example 5 was subjected to various characteristics tests with the polyester long fiber non-woven fabric-EVA film laminate C as the upper surface.

Comparative Example 1
Two PP long-fiber non-woven fabric-PE film laminates A were brought into contact with each other and laminated, and then bonded by thermocompression bonding to obtain a laminated sheet.

Comparative Example 2
The PP long-fiber non-woven fabric-PE film laminate A and the polyester long-fiber non-woven fabric-EVA film laminate C were brought into contact with each other and laminated, and were bonded by thermal pressure bonding to obtain a laminated sheet. The obtained laminated sheet was subjected to various characteristics tests with the PP long fiber non-woven fabric-PE film laminate A as the upper surface.

Comparative Example 3
The laminated sheet obtained in Comparative Example 2 was subjected to various characteristics tests with the polyester long fiber non-woven fabric-EVA film laminate C as the upper surface.

Comparative Example 4
The first PP long-fiber non-woven fabric B is coated with a modified asphalt melted by heating at a temperature of 160 ° C. with an average thickness of 0.2 mm using a die coater, and the coated modified asphalt has adhesiveness. While doing so, I tried to obtain a laminated sheet by laminating a second PP long fiber non-woven fabric B on the coated modified asphalt, but the PP long fiber of the coated modified asphalt Since the non-woven fabric B is often wetted, a laminated body in which the second PP long-fiber non-woven fabric B is adhered and not integrated is obtained. A laminate containing the second PP long-fiber non-woven fabric B (a laminate in which the second PP long-fiber non-woven fabric B was laminated in a non-adhesive state) was subjected to various tests.

Comparative Example 5
Asphalt roofing 940 specified in JIS A 6005 asphalt roofing felt was subjected to testing of various characteristics.

Table 1 shows the results of evaluating the laminated sheets obtained in Examples and Comparative Examples. The water resistance was evaluated only in some examples and comparative examples.

As is clear from the results in Table 1, the nail hole sealing property of the laminated sheet obtained in the examples was the same as that of the asphalt roofing 940 of Comparative Example 5 even though the unit area mass was small. Both passed. Furthermore, the asphalt wettability was low and the water resistance was high.

A scanning electron micrograph of the embossed recess of the laminated sheet obtained in Example 3 is shown in FIG. 1. Since the asphalt is supported by the polyethylene (PE) film, the embossed recess is not filled with asphalt and the embossed recess is not filled. The non-woven fabric provided with is not impregnated with asphalt. On the other hand, a scanning electron micrograph of the embossed recesses of the laminated sheet obtained in Comparative Example 4 is shown in FIG. 2. The embossed recesses are filled with asphalt, and the non-woven fabric having the embossed recesses is impregnated with asphalt.

Since the laminated sheet of the present invention has high waterproofness, it can be suitably used for covering the base of a building or a structure. In particular, the laminated sheet of the present invention has excellent nail hole sealing properties, and is therefore suitable for use in fixing to a base with nails, and is particularly suitable for under-roofing materials.

Claims (9)

Lamination including a waterproof layer containing asphalt, an intermediate layer laminated on at least one surface of the waterproof layer and non-porous, and a fiber layer laminated on the intermediate layer and which is a fibrous structure. A laminated sheet which is a hydrophobic non-woven fabric in which the fiber structure has a plurality of embossed recesses on the waterproof layer side . Laminated sheet according to claim 1, wherein the hydrophobic nonwoven fabric is a polypropylene long-fiber nonwoven fabric. The laminated sheet according to claim 1 or 2, wherein the intermediate layer contains a polyolefin resin. The laminated sheet according to any one of claims 1 to 3 , wherein the average thickness of the waterproof layer is 500 μm or less. The laminated sheet according to any one of claims 1 to 4 , wherein the waterproof layer does not include a fiber structure. The laminated sheet according to any one of claims 1 to 5 , wherein the unit area mass is 0.9 kg / m ^{2 or less.} The laminated sheet according to any one of claims 1 to 6, wherein an intermediate layer and a fiber layer are laminated on both sides of the waterproof layer, respectively. The laminated sheet according to any one of claims 1 to 7 , which is a waterproof sheet for covering the base of a building or a structure. The laminated sheet according to any one of claims 1 to 8 , which is an under-roofing material.

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