JP2000273419A - Tarpaulin - Google Patents

Abstract

(57) [Problem] To provide a waterproof sheet which is excellent in waterproofness and durability, has no environmental problems, is lightweight, and can be easily constructed for waterproofing roofs, rooftops, balconies and the like. SOLUTION: The waterproof sheet of the present invention has 1 to 1 carbon atoms.
100 parts by weight of an acrylic copolymer comprising 95 to 50% by weight of a (meth) acrylic acid alkyl ester having an alkyl group of 4 and 5 to 50% by weight of an olefin polymer having a polymerizable unsaturated double bond at a terminal; Tackifier 5 to 50
It is characterized in that a sealing agent consisting of parts by weight is laminated on an olefin-based resin sheet.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a waterproof sheet used for waterproofing roofs, rooftops, balconies, etc., in which a sealing agent having adhesiveness and self-fusing property is laminated on an olefin resin sheet.

[0002]

2. Description of the Related Art As a waterproofing method for roofs, rooftops, balconies and the like, asphalt waterproofing and sheet waterproofing are generally performed. Asphalt waterproofing is a method of coating a base material such as synthetic fiber non-woven fabric, glass fiber cloth, roofing base paper, mesh woven fabric, etc. and a hot asphalt on a ground surface, and has been used since ancient times for high reliability. It is a waterproof method. However, asphalt waterproofing has a major drawback in that smoke and odor are generated in the heating and melting step during construction.

[0003] In order to make up for the above disadvantages, modified asphalts which do not require an asphalt melting pot and do not generate smoke or odor have been developed. The modified asphalt is obtained by mixing 20 to 30% by weight of APP (atactic polypropylene) or SBS (styrene-butadiene-styrene block copolymer) into straight asphalt.

[0004] Waterproofing using modified asphalt is mainly performed by a torch method. In this method, a roofing sheet obtained by laminating a base material and a modified asphalt is adhered to a base surface while being heated and melted by a burner, and a joint between the sheets is also heated and fused by a burner. Asphalt roofing by such a torch method is particularly effective for perforated portions, and the connection portion has high waterproof reliability.

[0005] However, since APP-modified asphalt in the modified asphalt waterproofing has a relatively high softening temperature, the sheet becomes hard in winter and it is difficult to carry out the construction. Therefore, it is necessary to keep the sheet warm until immediately before construction. is there. On the other hand, SBS-modified asphalt has a relatively low softening temperature and is easier to perform in winter than an APP-based asphalt, but in summer, the sheet softens and walking resistance decreases.

In addition, since a burner is used for the construction, a training for LPG handling by a craftsman is required, and consideration for fire prevention is also required.

Further, a roofing sheet formed by laminating a plurality of modified asphalts and a base material becomes very heavy, and is required to be constructed in a place where a sufficient space cannot be ensured for deployment of the sheet or arrangement of burner equipment. Improper.

Waterproofing using a waterproofing sheet is a waterproofing method using a sheet obtained by rolling and molding a non-vulcanized rubber or a synthetic resin such as polyvinyl chloride, polyethylene, or polypropylene to a certain size. And an insulation method of attaching to a base using a fixing metal (for example, see Japanese Patent No. 2852477). As a sheet waterproofing sheet, a soft vinyl chloride resin sheet is mainly used. The vinyl chloride resin sheet is excellent in water resistance, weather resistance, and strength, and a highly reliable bonding structure can be obtained by bonding sheets together with an adhesive, welding with a solvent, or fusing by heating. Further, the synthetic resin sheet is relatively lightweight, does not require the use of an adhesive or a solvent at the connection portion, and can be performed in a narrow place without requiring special tools.

Waterproofing using synthetic rubber or synthetic resin sheets has become mainstream in relatively small-scale buildings such as detached houses and apartments by performing sealing treatment of connecting portions using an adhesive or a solvent. However, since the sheet waterproofing method uses an adhesive or a solvent, a curing period of several days is usually required until the waterproofing effect and the joining strength at the connection portion are completed.

Recently, the use of volatile materials has tended to be eliminated as much as possible in consideration of the health of craftsmen caused by adhesives and solvents. In addition, vinyl chloride resin, which is the mainstream of waterproof sheets, becomes a dioxin-generating substance when burned, which poses a problem for the environment.Therefore, incineration of offcuts and construction waste during construction has become a problem. There is a need for a waterproof sheet.

[0011]

DISCLOSURE OF THE INVENTION The present invention is excellent in waterproofness and durability, has no environmental problems, is lightweight, has a roof, a roof,
An object of the present invention is to provide a waterproof sheet that can be easily constructed for waterproofing a balcony or the like.

[0012]

SUMMARY OF THE INVENTION The present invention focuses on the excellent water stopping performance of a flexible acrylic resin having tackiness and self-fusing property, and proposes a waterproof sheet obtained by combining this with an olefin resin. As a result of conducting research to achieve this, the present invention has been achieved. That is, the waterproof sheet of the present invention is a (meth) acrylic acid alkyl ester 95 having an alkyl group having 1 to 14 carbon atoms.
A sealing agent consisting of 100 parts by weight of an acrylic copolymer comprising 5 to 50% by weight of an olefin polymer having a polymerizable unsaturated double bond at a terminal thereof and 5 to 50 parts by weight of a tackifier; It is characterized by being laminated on a base resin sheet.

The above acrylic copolymer has 1 to 2 carbon atoms.
(4) An alkyl (meth) acrylate having an alkyl group of 4 and an olefin polymer having a polymerizable unsaturated double bond at a terminal.

Examples of the alkyl (meth) acrylate having an alkyl group having 1 to 24 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, Isopropyl (meth) acrylate, n-butyl (meth) acrylate,
Sec-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate,
N-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, (meth) acryl Examples thereof include stearyl acid and isomiristyl (meth) acrylate, which may be used alone or in combination of two or more.

The olefin polymer having a polymerizable unsaturated double bond at the terminal is a polymer having a double bond copolymerizable with another polymerizable monomer at the terminal and a polymer structure having an olefin main skeleton. If it is not particularly limited, in consideration of the flexibility, adhesion and the like of the acrylic copolymer to be produced, the weight average molecular weight of the olefin polymer is preferably from 2,000 to 8,000, more preferably from 3,000 to 8,000. 6000. Weight average molecular weight 2
If it is less than 000, the effect of improving the adhesion to the low-polarity surface is reduced, and if it exceeds 8,000, the flexibility of the obtained acrylic copolymer is reduced.

Specific examples of the olefin main skeleton include:
Examples include an ethylene-butylene random copolymer and an ethylene-propylene copolymer. Commercially available ethylene-butylene random copolymers include, for example, "KLATON LIQUID Polymer" manufactured by Shell Chemical Company.
r HPVM-1253 "and the like.

The copolymerization ratio of the olefin polymer having a polymerizable unsaturated double bond at the terminal in the acrylic copolymer is 5 to 50% by weight, preferably 10 to 50% by weight.
35% by weight. When the copolymerization ratio of the olefin polymer is less than 5% by weight, the effect of improving the adhesion to the low-polarity surface is reduced, and when it exceeds 50% by weight, the copolymerization monomer solution gels and the copolymerization reaction becomes difficult.

The acrylic copolymer used in the present invention includes:
A tackifier is added to improve the adhesion to the low polarity surface. Examples of the tackifier include rosin-based resins, modified rosin-based resins, terpene-based resins, terpene-phenol-based resins, C5 and C9-based petroleum resins, cumarone resins, and hydrogenated products thereof. These may be used alone or in combination of two or more.

The amount of the tackifier to be added is 5 to 50 parts by weight, preferably 10 to 35 parts by weight, based on 100 parts by weight of the acrylic polymer. If the addition amount is less than 5 parts by weight, the effect of improving the adhesion to the low-polarity surface is small, and
If the amount exceeds 0 parts by weight, the glass transition temperature of the sealing agent increases, so that the flexibility is reduced, and the followability and adhesion to the gap having the uneven surface are reduced.

When the above tackifier is added to the photopolymerizable composition for polymerization, the polymerization rate may decrease or the molecular weight may decrease. Therefore, the amount of the chain transfer agent or the crosslinking monomer may be reduced. Is preferably adjusted appropriately. Further, it is preferable to select and use a tackifier having a low polymerization inhibition, and as the tackifier having a low polymerization inhibition, for example, a hydrogenated terpene resin, a hydrogenated rosin resin, a disproportionated rosin resin,
Alicyclic saturated hydrocarbon resins and the like can be mentioned.

Further, a copolymerizable monomer having an unsaturated double bond may be added in order to adjust the glass transition temperature, tackiness and the like of the obtained acrylic copolymer. Such copolymerizable monomers include, for example, styrene, α
-Styrene monomers such as -methylstyrene, o-methylstyrene, p-methylstyrene; carboxylic acid vinyl esters such as vinyl acetate; carboxylic acids having a vinyl group such as acrylic acid, methacrylic acid, maleic acid, phthalic acid and itaconic acid An anhydride of the carboxylic acid having a vinyl group;
Hydroxyl-containing vinyl monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, modified caprolactone (meth) acrylate, polyoxyethylene (meth) acrylate, and polyoxypropylene (meth) acrylate; Nitrogen-containing vinyl monomers such as (meth) acrylonitrile, N-vinylpyrrolidone, N-vinylcaprolactam, acryloylmorpholine, (meth) acrylamide, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, and dimethylaminopropyl acrylamide, and the like. And two or more of them may be used in combination.

As the amount of the copolymerizable monomer increases, the flexibility of the obtained sealing agent decreases, and the followability and adhesion to the uneven surface are reduced. On the other hand, the content is preferably 20% by weight or less.

The above-mentioned acrylic copolymer may be crosslinked as needed to improve heat resistance and creep characteristics. As a crosslinking method, for example, in a solution polymerization in which an acrylic copolymer is polymerized in a solvent or an emulsion polymerization in which water is polymerized in water, a polymerizable monomer having a reactive polar group is contained, and the polymer can react with the polar group. A method of crosslinking by adding a suitable crosslinking agent is exemplified.

Examples of the crosslinking agent include isocyanate-based crosslinking agents such as tolylene diisocyanate, naphthylene-1,5-diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, and trimethylolpropane-modified tolylene diisocyanate. Epoxy crosslinking agents such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether; aziridine such as N, N-hexamethylene-1,6-bis (1-aziridinecarboxamide) And the like. These may be used alone or in combination of two or more.

When the above acrylic polymer is polymerized by photopolymerization, crosslinking can be performed simultaneously with polymerization of the acrylic polymer by adding a polyfunctional (meth) acrylate compound as a crosslinking agent. it can.

Examples of the polyfunctional (meth) acrylate compound include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol di (meth) acrylate. Acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, glycerin methacrylate acrylate, pentaerythritol tri (meth) ) Acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene,
Epoxy (meth) acrylate, polyester (meth)
Acrylate, urethane (meth) acrylate and the like can be mentioned, and these may be used alone or in combination of two or more.

When the amount of the crosslinking agent is small, the cohesive force of the sealing agent is reduced and the heat resistance and the creep characteristics are inferior. When the amount is large, the flexibility is insufficient and the followability and adhesion to the uneven surface are reduced. The addition amount is preferably from 0.01 to 1% by weight, more preferably from 0.02 to 0.8% by weight, based on the copolymerization component of the acrylic polymer.

Various additives may be added to the sealing agent used in the present invention, if necessary. Examples of the additives include a plasticizer, a softening agent, an inorganic filler (arsium carbonate, silica, talc, etc.), an organic filler, a pigment,
Dyes and the like. The filler has an average particle size of 1
The apparent volume of the obtained sealing agent may be increased by adding 0 to 200 μm hollow microspheres, or by performing polymerization in a state where a gas is mixed and stirred with the copolymerization component syrup before polymerization.

As the inorganic filler, commercially available fillers such as calcium carbonate, silica and talc can be used. As the hollow microsphere, for example, a glass balloon “520FPS”
(PQ Corporation, average particle diameter 35 μm), glass balloon “Celstar Z27” (Asahi Glass Co., average particle diameter 65 μm) and the like.

The sealing agent used in the present invention can be obtained by a conventionally known polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization, and pearl polymerization. In the case of performing solution polymerization, a thermal polymerization initiator such as azobisisobutyronitrile and benzoyl peroxide is used in the presence of a solvent such as ethyl acetate and toluene. In the case of bulk polymerization, photopolymerization by UV (ultraviolet) is preferred because a uniform polymer is easily obtained, and a photopolymerization initiator is preferably used for photopolymerization.

In the polymerization method using ultraviolet rays, the polymerizable composition is cast on a substrate and irradiated with ultraviolet rays, so that the composition is obtained simultaneously with polymerization as a laminate with the substrate, so that productivity is excellent. Further, in addition to the fact that a thick sheet can be easily produced, there is also an advantage that deterioration of the environment due to evaporation of the solvent can be avoided because no solvent is used.

As the photopolymerization initiator, for example, 4-
(2-Hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone [Darocur 2 manufactured by Merck & Co., Ltd.
959 "], α-hydroxy-α, α'-dimethyl-acetophenone [“ Darocur 1173 ”manufactured by Merck & Co., Ltd.],
Methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone (“Irgacure 651” manufactured by Ciba-Geigy), 2-hydroxy-2-cyclohexylacetophenone (“Irgacure 18” manufactured by Ciba-Geigy)
Acetophenones such as 4 "; ketals such as benzyldimethyl ketal; and others, halogenated ketones, acylphosphinoxides, acylphosphonates and the like.

The addition amount of these photopolymerization initiators is 0.001 to 0.001 to the total amount of the acrylic copolymer monomers.
5% by weight is preferred. If the addition amount is less than 0.001% by weight, the monomer tends to remain because the reaction initiation density is insufficient, the heat resistance and adhesiveness of the sealing agent are reduced, and the monomer odor remains. On the other hand, if the amount exceeds 5% by weight, the reaction rate is increased, but the molecular weight of the polymer is reduced, and the performance and performance of the sealing agent may be varied or reduced.

The light source used for light irradiation in the photopolymerization preferably has a light emission distribution at a wavelength of 400 nm or less. Examples of the lamp having such a light emission distribution include a low-pressure mercury lamp, a medium-pressure mercury lamp, and a high-pressure mercury lamp. ,
Examples include an ultra-high pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, and a metal halide lamp. Among these, chemical lamps efficiently emit light in the active wavelength region of the photopolymerization initiator, and light is easily transmitted to the inside because there is little light absorption of components other than the photopolymerization initiator. Suitable for manufacturing.

The light irradiation intensity in the photopolymerization is a factor which affects the degree of polymerization of the obtained acrylic copolymer, and is appropriately determined depending on the intended performance. When using a cleavage type photopolymerization initiator having a normal acetophenone group, a wavelength region effective for photodecomposition of the photopolymerization initiator (depending on the photopolymerization initiator, usually 365 to 420 nm)
Is used as the light intensity of 0.1 to 10
0 mW / cm2 is preferred.

When the sealing agent is polymerized by photopolymerization, if the photopolymerization is performed in a state where the polymerizable composition is applied on the olefin resin sheet, the waterproof sheet of the present invention can be obtained simultaneously with the polymerization. Further, it is also possible to apply a polymerizable composition to a substrate having a releasing property, form a sealing agent by polymerization, and transfer this by laminating this to an olefin polymer sheet to form a waterproof sheet. is there.

As the olefin resin sheet, those generally used such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer and the like can be used. It is preferable to use one with improved workability in terms of workability.

Since the sealing agent of the present invention has excellent adhesiveness to metal, it is also possible to reliably waterproof joints of a steel sheet. As the adherend on which the waterproof sheet of the present invention is applied, polyethylene, polypropylene, and the like, and an olefin resin such as an ethylene-vinyl acetate copolymer containing these resins as a component, and a blend containing an olefin resin as a component Synthetic resins such as resins, galvanized steel sheets, galvanized steel sheets and other coated steel sheets, and colored steel sheets and the like coated steel sheets.

The waterproof sheet of the present invention is a strong adhesive laminate of a sealing agent and an olefin-based resin sheet and has high flexibility. The sealing agent has excellent adhesive properties, especially for olefin resins, which are considered to be difficult to bond, and has adhesiveness and self-fusing properties. In this part, the sheets are firmly adhered to each other by simply overlapping the waterproof sheets, and sufficient watertightness can be obtained. Furthermore,
Even if a small perforation occurs due to a nail or the like in the waterproof sheet, it exhibits self-healing properties that naturally fill the holes.

In the case where the connecting portions of the sheets intersect or have a T-shape, the waterproof sheet according to the present invention is a portion which is liable to be lifted or peeled off with time even if the conventional waterproof sheet is laminated and pasted. Due to the flexibility of the sealing agent and the olefin-based resin sheet, the sealing agent is tightly adhered to the adherend, and the self-fusing property of the sealing agent causes the sealing agents to be integrated with each other, so that floating and peeling over time do not occur.

For the construction of a rising portion from the floor surface on a balcony or a roof, a role cast using a steel plate or an olefin-based resin as a base material is used, and the joint between the role component and the structure is sealed with the waterproof sheet of the present invention. If the bonding is performed by using, the number of construction steps on site can be greatly reduced.

Since the waterproof sheet of the present invention uses acrylic resin and olefin resin and does not contain a halogen substance, there is no generation of harmful substances such as dioxin at the time of incineration, and there is no problem of environmental pollution. . Further, as compared with conventionally used asphalt-based materials and vinyl chloride-based resins, the weight is about two-thirds lighter, and it is easy to transport and handle at construction sites.

[0043]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the waterproof sheet of the present invention will be described. (Example 1) The following polymerizable composition was stirred until it was uniformly dispersed in a separable flask, and then nitrogen gas was bubbled to remove dissolved oxygen to obtain a polymerizable syrup. 7 parts by weight of acrylic acid 80 parts by weight of n-butyl acrylate 20 parts by weight of isononyl acrylate An ethylene-butylene random copolymer having a polymerizable unsaturated double bond at a terminal (“HPVM-1253” manufactured by Shell Co., Ltd.) 10 parts by weight Tackifying resin (alicyclic saturated hydrocarbon resin, manufactured by Arakawa Chemical Co., Ltd., trade name "Alcon P-100") 25 parts by weight n-dodecanethiol 0.02 parts by weight Hollow inorganic filler (manufactured by PQ Corporation) 7 parts by weight Crosslinking agent (hexanediol diacrylate) 0.05 parts by weight Photopolymerization initiator (2,2-dimethyl-2-phenylacetophenone, manufactured by Ciba Geigy Co., Ltd., trade name “IRGA Cure 651 ") 0.1 parts by weight

The polymerizable syrup was cast at a thickness of 1 mm on a polyethylene sheet having a thickness of 1 mm and subjected to a release treatment.
The ET film was coated such that the release-treated surface of the ET film was in contact with the polymerizable syrup. A chemical lamp whose height was adjusted so that the irradiation intensity on the PET film surface was ² mw / cm ² was arranged, and irradiation was performed with ultraviolet rays for 10 minutes to carry out polymerization to obtain a waterproof sheet with a release sheet. .

FIG. 1 is a cross-sectional view showing a state in which the waterproof sheet 1 is applied to an ALC floor of a flat roof or a balcony. A steel plate 4 having a foamed polystyrene insulation material 5 bonded thereto via a denatured silicone elastic adhesive 6 is laid on a base ALC plate 7, and joint portions of the steel plates 4 and 4 are so arranged that the acrylic flexible layer 12 is in contact with the surface of the steel plate 4. With the waterproof sheet 1. The end of the similar waterproof sheet 2 was overlapped on the end of the waterproof sheet 1 and the construction was completed.

(Example 2) FIG. 2 is a plan view showing a waterproof construction state at an intersection where a similar waterproof sheet 3 is further laminated on the laminated section of the waterproof sheet 1 and the waterproof sheet 2 shown in FIG. FIG. 3 is a sectional view taken along line III-III in FIG.

An acrylic tube having a height of 15 cm was placed around the overlapping portion of the waterproof sheet shown in Examples 1 and 2.
The gap between the lower end of the cylinder and the surface of the waterproof sheet was sealed with a silicone sealant and cured. Thereafter, water was put into the tube to a depth of 10 cm and left for 24 hours. Thereafter, the water and the cylinder were removed, the waterproof sheet was cut off, and the steel plate surface was observed. As a result, no water permeation was observed.

[0048]

The waterproof sheet of the present invention is a strong adhesive laminate of a sealing agent and an olefin-based resin sheet and has high flexibility. Even on the surface, it exhibits excellent adhesion and airtightness to objects such as metals to which oil such as cutting oil has adhered. Since the sealing agent has adhesiveness and self-fusing property, it is not necessary to cure the sheets simply by overlapping the waterproof sheets, and the sheets are firmly adhered to each other, and sufficient watertightness can be obtained. Furthermore, since it has a self-fusing property, it exhibits a self-healing property that naturally fills a hole even if a small perforation occurs. In addition, even when the connecting portions of the sheets intersect or have a T-shape, the sheets adhere tightly to the adherend without any gaps due to the flexibility, and the sealing agents are integrated with each other so that floating and peeling over time do not occur. Since the waterproof sheet of the present invention does not contain a halogen substance, there is no generation of harmful substances such as dioxin at the time of incineration treatment, and there is no problem of environmental pollution. In addition, it is easy to transport and handle at construction sites because it is lightweight without the skill of craftsmen,
It is suitably used for waterproofing roofs, rooftops, balconies and the like.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an embodiment in which a waterproof sheet according to the present invention is installed on a floor.

FIG. 2 is a sectional view showing another embodiment in which the waterproof sheet of the present invention is installed on a floor.

FIG. 3 is a sectional view taken along line III-III in FIG. 2;

[Explanation of symbols]

 1,2,3: waterproof sheet 4: steel plate 5: foamed polystyrene insulation material 6: modified silicone elastic adhesive 7: ALC plate 11,21,31: polyethylene sheet 12,22,32: sealing agent layer

Continued on the front page F term (reference) 4F100 AK03B AK04 AK71A BA02 BA07 CA16A EH46 GB90 JL00 JL03 4H017 AA04 AA31 AB01 AB07 AC04 AC16 AC17 AD06 AE03 4J004 AA01 AA04 AA10 AB01 CA04 CC02 FA10

Claims (1)

[Claims] 1. An alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms in an amount of 95 to 50% by weight.
And acrylic copolymer 100 comprising 5 to 50% by weight of an olefin polymer having a polymerizable unsaturated double bond at a terminal
A waterproof sheet characterized in that a sealing agent comprising 5 parts by weight and 5 to 50 parts by weight of a tackifier is laminated on an olefin-based resin sheet.