JPH0611537B2 - Waterproof layer - Google Patents

Description

The present invention relates to a waterproof layer for a roof of a building.

[Conventional technology and its problems]

2. Description of the Related Art Conventionally, waterproofing of flat roofs of buildings such as reinforced concrete condominiums and public corporation apartments has been carried out to carry out various waterproofing work such as asphalt waterproofing, mortar waterproofing, sheet waterproofing, and coating film waterproofing for the purpose of preventing water leakage. Particularly in recent years, with the progress of construction methods, waterproofing of coating film has shown remarkable growth. This has excellent workability such as easy construction of a complicated surface and a seamless waterproof layer.
Particularly in recent years, mainly in large cities, rooftop waterproofing construction for schools, buildings, condominiums, etc. is often performed, and sports facilities such as tennis and volleyball and playgrounds are often provided on top of it. Urethane-based waterproof materials are mainly used as those having waterproof performance and physical properties suitable for these purposes.

Generally, urethane-based waterproofing materials are solvent-free, so a thick coating can be obtained with a single application. It can be applied even in low temperatures in winter. The resulting coating has excellent water resistance and impact resilience. It has excellent characteristics such as large size, good walking feeling, and strong wear resistance. However, on the other hand, if there is uneven adhesion or air bubbles due to the dryness of the substrate and the degree of smoothness, and cracks occur in the substrate, zero span tension is applied to that part, causing creep rupture and water leakage problems. If it is wet, there is a defect that blisters are likely to occur due to peeling of the adhesive surface over time after construction. Furthermore, when repairing the existing asphalt exposure waterproofing, if urethane is directly applied to the asphalt waterproofing layer, the asphalt fraction will bleed, which will reduce the adhesion and contaminate the urethane waterproofing layer, making it sticky and terribly durable. Will fall. Therefore, it is necessary to completely remove the existing asphalt waterproof layer and prepare the ground with polymer cement mortar.

As a method for solving these drawbacks, improvement in adhesive strength, composite coating film waterproofing method using a reinforcing material and the like are generally adopted, but they are not yet satisfactory.

[Means for solving problems]

As a result of various studies to solve these problems, the present inventors have found excellent adhesion between unsaturated polyester resin having excellent water resistance and urethane resin, and arrived at the present invention.

That is, the present invention is a waterproof film layer comprising a lower layer composed of a cured product of an unsaturated monomer and an unsaturated polyester resin and an upper layer composed of a polyurethane resin.

The waterproof coating layer of the present invention is obtained by applying a mixture of an unsaturated monomer and an unsaturated polyester resin as a lower layer and curing it, and then applying and curing a polyurethane resin waterproofing material thereon, and cracks are generated in the base. It has a strong resistance to zero span tension and repeated fatigue in the case of being wet, does not cause blistering even if the base is wet, and has excellent walking feeling and good wear resistance. Further, the adhesion work does not decrease in the existing asphalt exposure waterproofing repair work, and bleeding due to the asphalt pool can be prevented.

The unsaturated polyester resin used in the present invention can be obtained by condensation and addition reaction of an alcohol compound and a carboxylic acid compound (including an acid anhydride and an alkyl ester compound of carboxylic acid). Among them, a diol component and a dicarboxylic acid are particularly preferable. Those derived from the components are preferred. More preferably, with respect to the total amount of dicarboxylic acid, it has an unsaturated acid of 1 to 25 mol% at the end, and does not contain an unsaturated bond in the chain of the unsaturated polyester resin, or even if it contains all dicarboxylic acid. It is preferable that the ratio of unsaturated carboxylic acid to If the amount of unsaturated acid at the terminal is more than 25 mol%, the elongation of the cured product will be remarkably reduced, the rubber elasticity will be impaired and it will become hard to follow the cracks in the base. If the amount of unsaturation at the end is less than 1 mol%, the number of cross-linking points in the unsaturated polyester resin will decrease, gelation will deteriorate, and stickiness will occur forever, resulting in poor adhesion to the urethane coating waterproof material of the top coat. . In addition, the amount of unsaturated bonds in the chain is 8.0
If it is more than mol%, the properties of the coating film become hard at low temperatures and the elongation is lost and becomes brittle.

The diol component is mainly composed of a dihydroxy compound, but may partially contain, for example, up to 20 mol% of a polyhydroxy compound such as a triol compound. In this case, for example, by adding a monohydroxy compound, the average is obtained. It is suitable to adjust the number of functional groups to correspond to the dihydroxy compound.

Examples of the dihydroxy compound include ethylene glycol, diethylene glycol, propylene glycol, aliphatic dialcohols such as 1,3 butanediol, 1,4 butanediol and neopentyl glycol, and alicyclic dihydroxy compounds such as 4,4-dihydroxydicyclohexylpropane. Examples thereof include aromatic dihydroxy compounds such as alkylene oxide adducts such as ethylene oxide or propylene oxide of bisphenol A.

Examples of the polyhydroxy compound include trimethylolpropane, glycerin, pentaerythritol and the like.

Examples of the monohydroxy compound include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-
Examples thereof include aliphatic monoalcohols such as butyl alcohol, iso-butyl alcohol and nonyl alcohol, alicyclic monoalcohols such as hexanol, and aromatic monoalcohols such as benzyl alcohol.

As carboxylic acid compounds, adipic acid, sebacic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid,
Saturated acids such as 3,6-endomethylene tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorphthalic anhydride and maleic anhydride, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, One or more unsaturated acids such as chlorinated maleic acid, acrylic acid and methacrylic acid are used.

The unsaturated monomer used in the present invention can be copolymerized with an unsaturated polyester resin, and is, for example, styrene, vinyltoluene, methyl (meth) acrylate, ethyl (meth).
Acrylate, isopropyl (meth) acrylate, n
-Butyl (meth) acrylate, iso-butyl (meth)
Acrylate, tert-butyl (meth) acrylate, n
-Octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (methyl) glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth)
There are acrylates and the like, and they are used alone or in combination of two or more. The use amount of these is 10 to 10 depending on the use application such as workability, flexibility, hardness, weather resistance, and solvent-based drying property.
It is in the range of 70% by weight.

A polymer compound, a plasticizer, and a curing catalyst (crosslinking initiator, crosslinking initiation auxiliary agent, etc.) can be added to the polyester resin as needed in order to improve the coating film performance and the curing speed. Polymer compounds that can be used are those that are mixed in order to reduce the manufacturing cost and improve the coating performance or coating performance when used as a coating material, such as acrylic resin, polyester resin, polyurethane resin, styrene. Examples thereof include allyl alcohol copolymer, polyethylene, wax and the like. Examples of the plasticizer include dioctyl phthalate, dibutyl phthalate, butyl phthalyl butyl glycolate, tricresyl phosphate, chlorinated paraffin and the like. In addition, bottom residues during petroleum refining such as asphalt and clean products such as coal tar can be added in order to improve coating film performance and improve compatibility with the base.

The curing new medium added as necessary can be appropriately selected depending on the curing method. When high energy such as electron beam is used, a polymerization initiator is not particularly required, but if light or ultraviolet ray is used, a well-known photosensitizer is necessary as a polymerization initiator, and if heat energy or far infrared ray is used. Benzoyl peroxide as a polymerization initiator, methyl ethyl ketone peroxide, ditersharibotyl peroxide, lauroyl peroxide, a suitable peroxide such as cumene hydroperoxide, a metal soap such as cobalt naphthenate as a polymerization initiation aid, Tertiary amines such as dimethylaniline, alcoholates such as sodium methylate, lauryl mercaptan, N-ethylmetatoluidine are suitable.

The urethane resin used in the present invention is obtained by reacting a two-component urethane prepolymer that reacts at room temperature with a curing agent, and the urethane prepolymer has an isocyanate group (-NCO) content of 2 to 10% by weight, Especially 3 to 6% by weight
It is preferable to use one of the following. If the isocyanate group content is less than 2% by weight, the physical properties of the coating film tend to deteriorate,
If it exceeds 10% by weight, it tends to foam to impair the function of the waterproof layer. As the curing agent, water, a polyether polyol containing propylene oxide as a main raw material, an aromatic amine, or the like is used alone or in combination of two or more.

A pigment such as carbon black or titanium white may be added to the curing agent, or a dispersant may be added to improve the dispersibility of the curing agent. Further, in addition to the antioxidant, antioxidant, and anti-settling agent, an organic salt of tin, lead, manganese, or the like can be added as a catalyst.

When the urethane prepolymer and the curing agent are used as a mixture, the ratio of active isocyanate groups in the urethane prepolymer to the active hydrogen equivalent of the curing agent is 1: 0.5 to 1: 1.5, especially 1: 0.
8 to 1: 1.2 is preferable.

In order to form the waterproof coating layer of the present invention, a mixture of an unsaturated monomer and an unsaturated polyester resin is used as a base with a rubber spatula, a brush,
It may be coated and cured by a usual coating means such as a construction tool such as a roller and mechanical coating such as spraying, and the mixture of the urethane prepolymer and the curing agent may be similarly applied and cured thereon.

If necessary, it may be combined with a textile product such as a woven fabric or a nonwoven fabric or a foamed plastic product for the purpose of further enhancing the effect of the waterproof layer. In this case, the textile product may be combined with either the polyester waterproof layer or the polyurethane waterproof layer, or with both, but in order to correspond to the movement of the base, the one combined with the lower polyester waterproof layer Is preferred.

Textile products include woven fabrics such as glass fibers, polyester fibers and vinylon fibers, and non-woven fabrics such as polyester fibers, and examples of foamed plastics include foamed polyethylene, foamed polypropylene and urethane foam.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, Reference Examples, and Comparative Examples, but the present invention is not limited thereto. In the following, parts are based on weight, unless otherwise specified.
The test results of the examples and comparative examples are summarized in the table.

Reference example-1 A concrete sidewalk with a thickness of 5 cm and dimensions of 30 x 30 cm for 1 day
It was dipped in water at 20 ° C, taken out, placed on wet sand, and water on the surface of the concrete sidewalk was wiped off with a waste cloth to pour water so that the sand did not dry to prepare a wet base material.

Reference example-2 Make a notch with a width of 1 mm and a depth of 5 mm on the back surface of the central part of the long side of an asbestos slate plate with dimensions of 400 mm × 200 mm and a thickness of 6 mm.
It was used as a test base material for repeated fatigue tests.

Comparative Example-1 100 parts of a urethane prepolymer containing polypropylene glycol and toluene diisocyanate as main components and having an active isocyanate group content of 5%, and 4,4 as a curing agent.
45 parts of methylene-bis-2-chloroaniline (MOCA),
335 parts of polypropylene glycol (molecular weight 3000) melted and heated, 500 parts of calcium carbonate, 100 parts of chromium oxide, 5 parts of lead octylate as a catalyst, 10 parts of Nocrac NBC (Ouchi Shinko KK) as an antioxidant, A polyurethane coating waterproof material (A) was obtained by mixing 5 parts of TSA-720 (Toshiba Silicone KK) as a foaming agent.

200 parts of polyurethane coating waterproof material (A) was weighed and applied with a rubber spatula to a thickness of 2 mm on the wet surface substrate prepared in Reference Example-1, and cured for 168 hours at 20 ° C while maintaining a wet condition. After that, the state of appearance was observed.

In addition, with the length of the asbestos slate plate prepared in Reference Example-2 set 50 mm apart from both ends in the longitudinal direction, apply polyurethane coating waterproof material (A) to a roller thickness of 3.0 mm for 168 hours. Cured at 20 ℃. Then, a tensile test was repeatedly performed in the same manner as in Example 1 described later.

In addition, apply the polyurethane coating waterproof material (A) to an asbestos slate plate with a size of 10 cm × 10 cm and a thickness of 5 mm to a thickness of 3 mm and apply the temperature at 20 ° C.
After curing for 168 hours, an abrasion test was conducted according to JIS K7204.

Also, release silicone TS M 650 on polyester film
(Toshiba Silicone KK) is applied, and then the polyurethane coating waterproof material (A) is applied to a thickness of 3 mm and cured at 20 ° C for 168 hours, then removed from the polyester film and rotated circularly with an inner diameter of 28.7 mm. A test piece was cut out using a blade, and at the time of testing, two sheets were piled up and a repulsion elasticity test was conducted according to JIS K6301.

Comparative Example-2 Diethylene glycol 10 was placed in a four-necked flask equipped with a stirrer, a thermometer, a condenser equipped with a condenser, and a nitrogen inlet tube.
7.8 parts, phthalic anhydride 74 parts, and maleic anhydride 49 parts were charged, and after esterification reaction at 210 ° C in a nitrogen stream, 0.05 parts of hydroquinone was dissolved in styrene 2
It was dissolved in 19.8 parts to obtain a pale yellow liquid.

To 100 parts of this pale yellow liquid, 40 parts of calcium carbonate and 10 parts of titanium white are uniformly mixed and dispersed at room temperature under high speed stirring, and 2.0 parts of benzoyl peroxide and 0.5 part of dimethylaniline are further mixed immediately before use to prepare an unsaturated polyester waterproof material.
I got (B).

Roll on the wet surface substrate prepared in Reference Example-1.
It was applied so as to have a thickness of 0 mm, and after curing for 168 hours at 20 ° C. while maintaining a wet state, the appearance was observed.

Also, with the asbestos slate board prepared in Reference Example-2 set 50 mm away from both ends in the longitudinal direction of the surface, apply unsaturated polyester waterproof material (B) with a roller to a thickness of 3.0 mm for 168 hours. It was dried and cured at 20 ° C. Then, the tensile test was repeated in the same manner as in Example-1.

Unsaturated polyester waterproof material (B) size 10 cm × 10 cm, thickness
Apply 3mm thickness on 5mm asbestos slate board, 20 ℃, 1
After 68 hours of dry curing, an abrasion test was conducted according to JIS K7204.

Also, release silicone TS M 650 on polyester film
(Toshiba Silicone KK) is applied, and then a polyurethane coating waterproof material (B) is applied on it to a thickness of 3 mm, cured at 20 ° C for 168 hours, then removed from the polyester film and rotated circularly with an inner diameter of 28.7 mm. A test piece was cut out using a blade, and at the time of testing, two sheets were piled up and a repulsion elasticity test was conducted according to JIS K6301.

Example-1 1,4 butanediol was added to a four-necked flask equipped with a stirrer, a thermometer, a condenser equipped with a condenser, and a nitrogen inlet tube.
Parts, 6.7 parts of citraconic acid anhydride were charged and reacted at a temperature of 120 ° C., then 131.4 parts of adipic acid and 7.0 parts of fumaric acid were added, and an esterification reaction was carried out at 210 ° C. in a nitrogen stream, followed by p-tertiarybutyl. A pale yellow liquid was obtained by dissolving 0.05 parts of catechol in 205 parts of styrene.

To 100 parts of this pale yellow liquid, 40 parts of calcium carbonate and 10 parts of titanium white are uniformly mixed and dispersed at room temperature under high speed stirring, and 2.0 parts of benzoyl peroxide and 0.5 part of dimethylaniline are further mixed immediately before use to prepare an unsaturated polyester waterproof material.
I got (C).

Using a roller on the wet surface substrate created in Reference Example-1
It was applied to have a thickness of 1.0 mm and cured at 168 hours at 20 ° C while maintaining a wet condition. After 3 hours of coating, apply the two-component reactive urethane waterproof material used in Comparative Example-1 with a rubber spatula to a thickness of 2 mm, and keep the wet state at 20 ° C for 168 hours. After curing, the appearance was observed.

Also, in the longitudinal direction of the surface of the asbestos slate board prepared in Reference Example-2, 50 mm apart from both ends, apply unsaturated polyester resin waterproof material (C) with a roller to a thickness of 1.0 mm, and paint 3 The polyurethane coating waterproof material (A) after the time
Was applied to a thickness of 2 mm with a rubber spatula and aged at 168 hours at 20 ° C. Before the test, with the coated surface of the test piece facing down, both ends in the longitudinal direction were supported by spacers with a plate thickness of about 4 mm, and the asbestos slate board was cracked by lightly pressing the center part so as not to damage the coating film. Later, hydraulic servo fatigue tester (K.
In K.), a tensile test was repeatedly conducted from 0 to 3 mm in elongation width with a cycle of about 6 seconds.

Also, measure the unsaturated polyurethane waterproof material (C) with dimensions of 10 cm x 10 cm,
Apply 1mm thickness on a 5mm thick asbestos slate board, and after 3 hours of coating, apply the above polyurethane coating waterproof material (A) to 2mm thickness with a rubber spatula and cure at 20 ℃ for 168 hours. JIS K
A wear test was performed according to 7204.

Also, release silicone TSM 650 on polyester film
(Toshiba Silicone KK) is applied, polyurethane coating waterproof material (A) is applied on it with a thickness of 3 mm, and after 3 hours of application, polyurethane coating waterproof material (C) is applied with a rubber spatula to a thickness of 2 mm. After drying and curing for 168 hours at ℃, detach from the polyester film, cut out the test piece using a circular rotary blade with an inner diameter of 28.7 mm, and stack the two test pieces during the test so that the impact end touches the polyurethane coating. The impact resilience test was conducted according to JIS K6301.

Example-2 Diethylene glycol was added to a four-necked flask equipped with a stirrer, a thermometer, a condenser equipped with a condenser, and a nitrogen inlet tube.
After charging 3.4 parts and maleic anhydride 3.9 parts and reacting at a temperature of 120 ° C., sebacic acid 173.7 parts and mesaconic acid 13.0
After adding 0.1 part of the mixture and conducting an esterification reaction at 210 ° C. in a nitrogen stream, 0.05 part of hydroquinone was dissolved in 268 parts of dissolved styrene to obtain a pale yellow liquid. To 100 parts of this pale yellow liquid, 10 parts of calcium carbonate and 5 parts of titanium white were uniformly mixed and dispersed at room temperature under high speed stirring. Immediately before use, 2.0 parts of benzoyl peroxide and 0.5 part of paratoluidine were added to the unsaturated polyester resin waterproof material (D).
Got

Unsaturated polyester waterproof material used in Example-1
In the same manner as in Example 1 except that the unsaturated polyester waterproof material (D) was used instead of (C), the appearance of the coating film after curing, repeated fatigue, abrasion resistance and impact resilience were measured in a wet state.

Example-3 Unsaturated polyester waterproof material used in Example-1
The appearance of the coating film after curing in a wet state, repeated fatigue, and abrasion resistance in the same manner as in Example-1 except that the unsaturated polyester waterproof material (B) prepared in Comparative Example-2 was used instead of (C). sex,
The impact resilience was measured.

[Effects of the Invention] As is clear from the examples, when a waterproof layer consisting of a polyurethane resin or a polyester resin alone is applied to a wet surface, swelling or pinholes occur, or the physical properties are poor.
On the other hand, the waterproof layer of the present invention does not have such drawbacks and is extremely suitable as a waterproof layer for a roof.

Claims (2)

[Claims] 1. A waterproof coating layer comprising a lower layer composed of a cured product of an unsaturated monomer and an unsaturated polyester resin and an upper layer composed of a polyurethane resin. 2. An unsaturated polyester resin containing 1 to 25 mol% of an unsaturated acid at a terminal and 8 mol% or less of an unsaturated acid in a chain with respect to the total amount of a dicarboxylic acid. The coating film waterproof layer according to claim 1.