JPH0444571B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a waterproof sheet, and more particularly to a waterproof sheet for buildings, etc., which has excellent weather resistance and appearance, and prevents expansion due to water vapor and air. [Problems to be solved by the prior art and the invention] In concrete and mortar buildings, etc.
Various waterproof sheets are used to protect against rainwater, and are made of a composition consisting of hydroxyl group-containing liquid polybutadiene, a polyisocyanate compound, and asphalt, and have linear (groove-like) uneven shapes on the surface that adheres to buildings. A cured sheet having the following is known. This waterproof sheet is preferable because water vapor and air escape from the concave grooves and prevent the sheet from expanding. However, the surface that comes in contact with the outside air has poor weather resistance, and it deteriorates and cracks after long-term use. There were drawbacks such as: [Means for Solving the Problems] An object of the present invention is to provide a waterproof sheet that solves the above problems. That is, the present invention comprises at least two layers: a layer (A) of a plastic sheet or metal foil, and a layer (B) of a cured product of a composition comprising a hydroxyl group-containing liquid diene polymer, a polyisocyanate compound, and a bituminous substance. The present invention provides a waterproof sheet which is formed from a laminate, and is characterized in that the layer (A) is disposed on the surface that is in contact with the outside air, and that both surfaces of the laminate are provided with an uneven shape. Various materials can be used as the plastic sheet constituting layer (A) in the present invention, but thermoplastic resin sheets such as polyolefin sheets such as polyethylene and polypropylene, and methyl methacrylate-styrene-acrylonitrile copolymer sheets are preferred. It is. Further, various metal foils can be used, but aluminum foil, stainless steel foil, etc. are preferable. The thickness of this layer (A) is usually 1μ~
0.5mm, preferably 30μ to 0.3mm. Next, the components constituting layer (B) will be explained. The hydroxyl group-containing liquid diene polymer is a liquid diene polymer having a hydroxyl group in the molecule, preferably at the end of the molecule, and having a number average molecular weight of 300 to 25,000, preferably 500 to 10,000. These liquid diene polymers include diene polymers with 4 to 12 carbon atoms, diene copolymers, and diene monomers with 2 carbon atoms.
-22 copolymers with α-olefinic addition polymerizable monomers, etc. Hydroxyl group content is 0.1~
10 meq/g, preferably 0.3 to 0.5 meq/g.
Specifically, butadiene homopolymer, isoprene homopolymer, butadiene-styrene copolymer, butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, butadiene-2-ethylhexyl acrylate copolymer,
Examples include butadiene-n-octadecyl acrylate copolymer. These liquid diene polymers can be produced, for example, by subjecting a conjugated diene monomer to a heating reaction in a liquid reaction medium in the presence of hydrogen peroxide. In addition, a polyisocyanate compound is an organic compound having two or more isocyanate groups in one molecule, and is an organic compound having two or more isocyanate groups in one molecule. Contains reactive isocyanate groups. Examples of polyisocyanate compounds include the usual aromatic, aliphatic and cycloaliphatic ones, such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate (MDI), liquid modified diphenyl Examples include methane diisocyanate, polymethylene polyphenyl isocyanate, xylylene diisocyanate, cyclohexyl diisocyanate, cyclohexane phenylene diisocyanate, naphthalene-1,5-diisocyanate, isopropylbenzene-2,4-diisocyanate, polypropylene glycol and tolylene diisocyanate addition reaction product, etc. ,
Particularly preferred are MDI, liquid modified diphenylmethane diisocyanate, tolylene diisocyanate, and the like. There is no particular restriction on the blending ratio of the above hydroxyl group-containing liquid diene polymer and polyisocyanate compound, but usually the molar ratio of the hydroxyl group (OH) of the hydroxyl group-containing liquid diene polymer to the isocyanate group (NCO) of the polyisocyanate compound is is NCO/OH=0.2
-10.0, preferably 0.5-6.0. If the blending ratio of both is outside this range, curing becomes difficult, which is not preferable. Next, the bituminous substance is not particularly limited, and examples thereof include petroleum asphalt such as straight asphalt, blown asphalt, semi-blown asphalt, and fropan (solvent) deasphalt, petroleum pitch, coal tar, and coal pitch. The bituminous substance is used in an amount of 10 to 1000 parts by weight based on 100 parts by weight of the hydroxyl group-containing liquid diene polymer. Furthermore, polyol compounds, polyamine compounds, and other various additives can be added as components constituting the layer (B) of the present invention. Various polyol compounds can be used, and any of primary polyols, secondary polyols, and tertiary polyols may be used. Specifically, for example, 1,2-propylene glycol,
Dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-pentanediol, 2,3-pentanediol, 2,5-hexanediol,
2,4-hexanediol, 2-ethyl-1,3
-hexanediol, cyclohexanediol,
Hydroxyl group bonded to at least one secondary carbon such as glycerin, N,N'-bis-2-hydroxypropylaniline, N,N'-bishydroxyisopropyl-2-methylpiperazine, propylene oxide adduct of bisphenol A Examples include low molecular weight polyols containing. Furthermore, as a polyol, ethylene glycol containing no hydroxyl group bonded to a secondary carbon, 1,3
-Propylene glycol, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc. can also be used. Diols are usually used as the polyols used in the present invention, but triols and tetraols may also be used, and their molecular weights range from 50 to 500. Further, the polyamine compound is not particularly limited and may be any of diamine, triamine, and tetraamine. Furthermore, any one of primary polyamine, secondary polyamine, and tertiary polyamine can also be used. Examples of polyamine compounds include aliphatic amines such as hexamethylene diamine; 3.
Alicyclic amines such as 3'-dimethyl 4,4'-diaminodicyclohexylmethane; aromatic amines such as 4,4'-diaminodiphenyl; tetramines such as 2,4,6-tri(dimethylaminomethyl)phenol, etc. can be mentioned. The appropriate amount of the polyol or polyamine to be blended is 1 to 1000 parts by weight, preferably 3 to 200 parts by weight, per 100 parts by weight of the hydroxyl group-containing liquid diene polymer. In addition, mica, graphite, vermiculite, calcium carbonate, slate powder, etc. are added as fillers, plasticizers such as dioctyl phthalate are added as viscosity modifiers, aromatic, naphthenic,
Softeners such as paraffin oil can be added, and alkyl phenol resins, terpene resins, terpene phenol resins, xylene formaldehyde resins, rosins, hydrogenated rosins, coumaron resins, aliphatic and aromatic resins can be added to adjust adhesive strength and adhesion. Tackifying resins such as family petroleum resins can also be added.
Further, curing accelerators such as diphthyltin dilaurate, stannous octoate, and polyethylene diamine can also be added. Furthermore, an anti-aging agent can be added to improve weather resistance, and a silicon compound or the like can be added as an antifoaming agent. Although the above composition is in liquid form, the conditions for curing this composition vary depending on the type and amount of each component used, but are usually at a temperature of 0 to 200°C, preferably 15 to 150°C. It may be heated for 5 minutes to 168 hours, preferably 30 minutes to 96 hours. The thickness of layer (B) is suitably 0.1 to 10 mm, preferably 0.5 to 5 mm. The waterproof sheet of the present invention includes the above layers (A) and (B), and can be used by laminating other layers as necessary. Here, various layers can be used as the other layer, and it may be any one of the above layers. However, it is necessary to arrange the layer (A) on the surface that is in contact with the outside air. For example, layer (A) can be laminated below layer (B) of a waterproof sheet consisting of layers (A) and (B). The thickness of the layer to be added in this case may be determined appropriately considering the purpose of use, etc., but when layer (A) is laminated as described above, the thickness is 1 μ to 0.5 mm, preferably 30 μ
~3 mm is appropriate. Further, in the waterproof sheet of the present invention, both sides of the laminate, that is, the surface in contact with the building (building surface)
The surface in contact with the outside air (the outside air surface) has an uneven shape (preferably embossed) on both sides. In this case, it is preferable that the surface of the building has linear (groove-like) unevenness in order to discharge water vapor and air. Further, the uneven shape of the outside air surface may be either linear or dotted, and by providing the outside air surface with an uneven shape, the appearance becomes beautiful and the effect of preventing slipping during walking is exhibited. [Effects of the Invention] The waterproof sheet of the present invention has excellent weather resistance and a beautiful appearance, and also has the effect of preventing the sheet from expanding due to water vapor or air.
Therefore, it is useful in fields such as waterproofing construction of buildings. [Example] Next, the present invention will be explained in detail with reference to Examples. Example 1 80 parts by weight of straight asphalt (penetration 60/80) was heated to 135°C, and liquid polybutadiene containing terminal hydroxyl groups (manufactured by Idemitsu Petrochemical Co., Ltd., "R-
45HT", number average molecular weight 2800, hydroxyl group content
0.8 meq/g) and 2.1 parts by weight of diphenylmethane diisocyanate were added and mixed.
At this time, the temperature of the composition was 120°C. This liquid composition was applied to a thickness of 2 mm on a 0.05 mm thick aluminum foil (on which dotted irregularities were formed by embossing). This laminate was cured and bonded by heating at 7° C. for 45 hours. Next, linear unevenness was formed on the surface of the cured composition by embossing. A xenon weather meter (manufactured by Toyo Seiki Seisakusho Co., Ltd., Weather-O-Meter,
Lamp) temperature 40℃, humidity 60%RH (cycle 102
-18) After irradiating for 1000 hours, the appearance was evaluated, and the cured composition layer was cut out and JIS K6301
Physical properties were measured. The results are shown in Table 1. Example 2 The liquid composition in Example 1 was applied to a thickness of 2 mm on a 0.2 mm thick polypropylene sheet embossed into dots, and the liquid composition was embossed into lines to a thickness of 2 mm. A 0.2mm polypropylene sheet was attached. The intermediate layer was cured by heating this laminate at 50° C. for 48 hours. The dotted embossed surface of the obtained waterproof sheet was irradiated with the lamp in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 1. Comparative Example A waterproof sheet was obtained in the same manner as in Example 1 except that the aluminum foil was not used in Example 1. Table 1 shows the measurement results of the physical properties of this sheet.

[Table] * Many cracks occur on the surface

[Brief explanation of drawings]

1 and 2 are cross-sectional views of embodiments of the present invention. A: layer (A), B: layer (B).

Claims (1)

[Claims] 1. A layer (A) of a plastic sheet or metal foil;
It is formed of a laminate consisting of at least two layers, including a layer (B) of a cured product of a composition consisting of a hydroxyl group-containing liquid diene polymer, a polyisocyanate compound, and a bituminous substance, and the layer (A) is exposed to outside air. A waterproof sheet, characterized in that it is disposed on a surface in contact with the laminate, and has an uneven shape on both sides of the laminate. 2. The sheet according to claim 1, wherein the uneven shape formed on one surface of the laminate that is in contact with the building is a linear shape formed by embossing.