JPS63126746A - Coated film waterproof layer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a waterproof layer for the roof of a building.

[Conventional technology and its problems]

Conventionally, various types of waterproofing work such as asphalt waterproofing, mortar waterproofing, sheet waterproofing, and paint film waterproofing have been carried out to waterproof the flat roofs of buildings such as reinforced concrete condominiums and public corporation apartments, and to prevent water leakage. Particularly in recent years, with the advancement of construction methods, the use of waterproof coatings has shown remarkable growth. This method is extremely easy to work with, as it can be easily applied to complex-shaped surfaces and provides a seamless waterproof layer. Particularly in recent years, especially in large cities, rooftop waterproofing work has been carried out on schools, buildings, condominiums, etc., and sports facilities such as tennis and volleyball, as well as play areas, are often built on top of the rooftops.
Urethane waterproof materials are mainly used as they have waterproof performance and physical properties suitable for these purposes.

In general, urethane-based waterproof coating materials are solvent-free, so a thick coating can be obtained with a single application, and can be applied even at low temperatures in winter.The resulting coating has excellent water resistance and rebound resilience. It has excellent features such as a large diameter, good walking feel, and resistance to abrasion.

However, on the other hand, depending on the dryness and smoothness of the base, uneven adhesion and bubbles may occur, cracks may occur in the base, creep rupture occurs due to zero span tension being applied to that part, water leakage troubles occur, and the base If the adhesive is damp, there are disadvantages such as the tendency for the adhesive surface to peel off and cause blisters over time after installation. Furthermore, when repairing existing exposed asphalt waterproofing, applying urethane directly to the asphalt waterproofing layer will cause the asphalt reservoir to bleed, reducing adhesion and contaminating the urethane waterproofing layer, making it extremely sticky and significantly reducing its durability. Therefore, it is necessary to completely remove the existing asphalt waterproof layer and prepare the base with polymer cement mortar.

As a method to solve these drawbacks, improvements in adhesive strength, composite coating waterproofing methods using reinforcing materials, etc. have generally been adopted, but these methods are still not satisfactory.

[Means for solving problems]

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

That is, the present invention is a waterproof coating layer consisting of a lower layer made of a cured product of an unsaturated monomer and an unsaturated polyester resin, and an upper layer made of a polyurethane resin.

The waterproof coating layer of the present invention is obtained by applying and curing a mixture of an unsaturated monomer and an unsaturated polyester resin as a lower layer, and then applying and curing a polyurethane resin waterproofing material on top of the mixture, which causes cracks in the base layer. It has strong resistance to zero-span tension and repeated fatigue when exposed to water, does not blister even when the base is damp, has a good walking feel and has good abrasion resistance, and can be used to repair existing asphalt exposed waterproofing. With this method, it is possible to prevent bleeding caused by asphalt storage without reducing the adhesion force.

The unsaturated polyester resin used in the present invention can be obtained by the condensation and addition reaction of an alcohol compound and a carboxylic acid compound (including acid anhydrides and carboxylic acid alkyl ester compounds). Those derived from components are preferred, and more preferably 1 to 25 dicarboxylic acids at the terminal based on the total amount of dicarboxylic acid.
mol% of unsaturated acids, and the unsaturated polyester resin has no unsaturated bonds in its chains, or even if it does contain unsaturated bonds, the ratio of unsaturated carboxylic acids to the total dicarboxylic acids is 8.
The amount of terminal unsaturated acid is preferably 0 mol% or less. If the amount of terminal unsaturated acid is more than 25 mol%, the elongation of the cured product will be significantly reduced, the rubber elasticity will be impaired, and it will become hard and unable to follow cracks in the base. If the amount of saturated acid is less than 1 mol%, the number of crosslinking points in the unsaturated polyester resin will decrease, resulting in poor gelation, persistent stickiness, and poor adhesion to the top coat urethane coating waterproof material. If the amount of unsaturated bonds in the chain is more than 8.0 mol %, the coating film becomes hard at low temperatures, loses its elongation, and becomes brittle.

The diol component mainly consists of dihydroxy compounds, but may also partially contain, for example, up to 20 mol% of polyhydroxy compounds such as triol compounds; in this case, for example, by incorporating a monohydroxy compound, the average It is appropriate to adjust the number of functional groups to be equivalent to that of a dihydroxy compound.

Examples of dihydroxy compounds include aliphatic dialcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1.3-butanediol, 1.4-butanediol, and neopentyl glycol; alicyclic dihydroxy compounds such as 4,4-dihydroxydicyclohexylpropane; Examples include aromatic dihydroxy compounds such as alkylene oxide adducts of bisphenol A such as ethylene oxide or propylene oxide.

Examples of polyhydroxy compounds include trimethylolpropane, glycerin, and pentaerythritol.

Examples of monohydroxy compounds include aliphatic monoalcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, 1so-butyl alcohol, and nonyl alcohol, alicyclic monoalcohols such as hexanol, and aromatic monoalcohols such as benzyl alcohol. Alcohol is an example.

Carboxylic acid compounds include adipic acid, sepatic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid,
3.6-Nindomethylenetetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,
One or more saturated acids such as talic acid (tetrachloroanhydride) or unsaturated acids such as maleic anhydride, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, chlorinated maleic acid, acrylic acid, methacrylic acid, etc. Two or more types are used.

The unsaturated monomer used in the present invention is one that can be copolymerized with the unsaturated polyester resin, such as styrene, vinyltoluene, methyl (meth)acrylate, ethyl (meth)acrylate, etc.
acrylate, isopropyl (meth)acrylate, n
-Butyl (meth)acrylate, 1so-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)acrylate, etc., and these are used singly or in combination of two or more. The amount of these used is in the range of 10 to 70% by weight depending on the intended use such as workability, flexibility, hardness, weather resistance 1, and solvent drying property.

Such polyester resins contain polymer compounds, plasticizers, curing catalysts (in order to improve coating performance and speed up curing).
A crosslinking initiator, a crosslinking initiation aid, etc.) can be added as necessary. Polymer compounds that can be used include:
It is mixed to reduce manufacturing costs or improve coating performance or coating performance when used as a coating material, such as acrylic resin, polyester resin, polyurethane resin, styrene-allyl alcohol copolymer, polyethylene. Alternatively, wax etc. can be mentioned. Examples of the plasticizer include dioctyl phthalate, dibutyl phthalate, butylphthalyl butyl glycolate, tricresyl phosphate, and chlorinated paraffin. In addition, bottom residues from petroleum refining such as asphalt and pickled substances such as coal tar can be added to improve coating performance and compatibility with the base.

The curing catalyst added as necessary can be appropriately selected depending on the curing method. A polymerization initiator is not particularly required when using high energy such as an electron beam, but a well-known photosensitizer is required as a polymerization initiator when using light or ultraviolet rays, and when using thermal energy or far infrared rays, a polymerization initiator is not required. Peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide, ditertiary butyl peroxide, lauroyl peroxide, and cumene hydroperoxide are suitable as polymerization initiators, and metal soaps such as cobalt naphthenate and dimethyl are suitable as polymerization initiators. Tertiary amines such as aniline, alcoholades such as sodium methylate, lauryl mercaptan, N-ethyl metatoluidine, etc. are suitable.

The urethane resin used in the present invention is made by reacting a two-component urethane prepolymer that reacts at room temperature with a curing agent, and the urethane prepolymer has an incyanate group (-NGO) content of 2 to 10. % by weight, especially 3-6
It is preferable to use % by weight. If the isocyanate group content is less than 2% by weight, the physical properties of the coating film tend to deteriorate, and if it exceeds 10% by weight, it tends to foam and impair the function of the waterproof layer. As the curing agent, water, polyether polyol containing propylene oxide as a main raw material, aromatic amine, etc. may be 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. Furthermore, in addition to anti-aging agents, antioxidants, and anti-settling agents, organic salts such as tin, lead, manganese, etc. can also be added as catalysts.

When using a mixture of urethane prepolymer and curing agent, the active hydrogen equivalent ratio of the active isocyanate group of the urethane prepolymer to the curing agent is 1:0.5 to 1:1.5, especially 1.
:0.8-1:1.2 is preferable.

To form the waterproof layer of the coating film of the present invention, a mixture of an unsaturated monomer and an unsaturated polyester resin is added to the base by using a rubber spatula, brush, etc.
It may be coated and cured using an ordinary coating method such as a construction tool such as a roller or a mechanical coating such as a spray, and then a mixture of a urethane prepolymer and a curing agent may be similarly applied thereon and cured.

If necessary, the waterproof layer may be combined with a textile product such as a woven fabric or a nonwoven fabric or a foamed plastic product in order to further enhance the effect of the waterproof layer. In this case, the textile product may be combined with either a polyester waterproof layer, a polyurethane waterproof layer, or both, but in order to support the movement of the underlying layer, it is preferable to combine it with the lower polyester waterproof layer. is preferred.

Examples of fiber products include woven fabrics such as glass fibers, polyester fibers, and vinylon fibers, and nonwoven fabrics such as polyester fibers, and examples of foamed plastics include foamed polyethylene, foamed polypropylene, and foamed urethane.

〔Example〕

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

Reference example-1 A concrete sidewalk board with a thickness of 5 cm and dimensions of 30 x 30 C1 was immersed in water at 20°C for one day, taken out, placed on wet sand, and the moisture on the surface of the concrete sidewalk board was gently wiped off with a rag. Water was added to create a wet base material to prevent it from drying out.

Reference Example-2 A notch with a width of 11 and a depth of 5a+m was made on the back surface of an asbestos slate plate having dimensions of 400+sw+ x 200+wm and a thickness of 6mm at the center in the longitudinal direction, and was used as a test base material for a cyclic fatigue test.

Comparative Example-1 100 parts of a urethane prepolymer with an active incyanate group content of 5% containing polypropylene glycol and toluene diisocyanate as main ingredients, and 4 parts as a curing agent.
．． 4-methylene-bis-2-chloroaniline (MOC^
) 45 parts, polypropylene glycol (molecular weight 300G
) 335 parts melted and heated, 500 parts of calcium carbonate, 100 parts of chromium oxide, 5 parts of lead octylate as a catalyst, 10 parts of Tsukurak NaC (Niuchi Shinko, Ni,) as an anti-aging agent, and 10 parts of antifoaming agent. TSA-720
(Toshiba silicone) was mixed with 5 parts to obtain a polyurethane coating waterproofing material (A).

Weighed 200 parts of polyurethane coating waterproofing material (A), applied it to a thickness of 211II11 with a rubber spatula on the wet surface base prepared in Reference Example-1, and cured it at 20'C for 168 hours while keeping it moist. After that, the appearance condition was observed.

Further, on the surface of the asbestos slate board prepared in Reference Example-2, 50 mm away from both ends in the longitudinal direction, a polyurethane coating waterproofing material (A) was applied with a roller to a thickness of 3.01 cm. It was cured at 20°C for an hour. Thereafter, a repeated tensile test was conducted in the same manner as in Example-1 described below.

Also, polyurethane coating waterproof material (A) with dimensions 10cm x 1
0 cm, 3 mm on a 511 part m thick asbestos slate board.
Apply to a thick layer and dry and cure at 20°C for 168 hours to apply JI.
A wear test was conducted according to SK7204.

In addition, release silicone TSM 6 is applied to the polyester film.
50 (on Toshiba silicone), and on top of that, apply a polyurethane coating waterproofing material (A) to a thickness of 3 mm,
After curing at 20°C for 168 hours, it was removed from the polyester film, and a test piece was cut out using a circular rotary blade with an inner diameter of 28.7+n. During the test, two pieces were stacked and a rebound resilience test was conducted according to JIS K6301. .

Comparative Example-2 Diethylene glycol 10 was placed in a four-loaf flask equipped with a stirrer, thermometer, fractionator with condenser, and nitrogen inlet tube.
7.8 parts, phthalic anhydride 74 parts, maleic anhydride 4
After esterification reaction was carried out at 210° C. in a nitrogen stream, 0.05 part of hydroquinone was dissolved in 219.8 parts of styrene 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 were uniformly mixed and dispersed at room temperature under high-speed stirring, and immediately before use, 2.0 parts of benzoyl peroxide and 0.5 parts of dimethylaniline were added. A saturated polyester waterproof material CB) was obtained.

3 with a roller on the wet surface base created in Reference Example-1
．． Apply to a thickness of 0 mm and apply at 20° for 168 hours.
After curing while maintaining a moist state at C, the external appearance was observed.

In addition, unsaturated polyester waterproofing material (B) was applied with a roller to a thickness of 3.0 mm on the surface of the asbestos slate board prepared in Reference Example 2 at a distance of 501II11 from both ends in the longitudinal direction, and 168 It was dried and cured at 20°C for an hour. Thereafter, a repeated tensile test was conducted in the same manner as in Example-1.

Unsaturated polyester waterproofing material (B) with dimensions 10cm x 10
3II1 on an asbestos slate board of cm, thickness 5Ilffi
Apply to 1 thickness and dry and cure at 20°C for 168 hours.
A wear test was conducted according to IS K1204.

In addition, release silicone TSM 6 is applied to the polyester film.
50 (Toshiba Silicone L1 [,)] was applied, and a polyurethane film waterproofing material (B) was applied thereon to a thickness of 3111fi, and after curing at 20°C for 168 hours, it was removed from the polyester film and the inner diameter was 28. A test piece was cut out using a circular rotary blade of .711II11, and during the test, two pieces were stacked and a rebound resilience test was conducted according to JIS K6301.

Example-1 1,4-butanediol was placed in a four-bottle flask equipped with a stirrer, a thermometer, a fractionator with a condenser, and a nitrogen inlet tube 9
6.3 parts and 6.7 parts of citraconic anhydride were added, and the temperature was 1.
After reacting at 20°C, 131.4 parts of adipic acid and 7.0 parts of fumaric acid were added and esterification was carried out at 210°C in a nitrogen stream, followed by 0.05 part of p-tert-butylcatechol. was dissolved in 205 parts of styrene 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 were uniformly mixed and dispersed at room temperature under high-speed stirring, and immediately before use, 2.0 parts of benzoyl peroxide and 0.5 parts of dimethylaniline were added. A saturated polyester waterproof material (C) was obtained.

1 with a roller on the wet surface base created in Reference Example-1
, applied to a thickness of 0 ma+, 168 hours, 2
After 3 hours of 1° painting and curing while keeping it moist at 0°C, apply the two-component reactive urethane waterproofing material used in Comparative Example-1 on top of it using a rubber spatula to a thickness of 2mm+. After coating and curing for 168 hours while maintaining a moist state at 20°C, the external appearance was observed.

In addition, unsaturated polyester resin waterproofing material (C) was applied with a roller to a thickness of 1.0 mm at a distance of 50 m + * from both ends in the longitudinal direction of the surface of the asbestos slate board prepared in Reference Example-2. 3 hours after painting, apply the above polyurethane coating waterproofing material (A) to a thickness of 2 mm with a rubber spatula,
It was cured at 20°C for 68 hours. Before the test, the asbestos slate board was split by placing the test piece with the coated side facing down, supporting both longitudinal ends with spacers approximately 4 mm thick, and applying light pressure to the center to avoid damaging the paint film. Afterwards, a tensile test was repeatedly performed with a hydraulic servo fatigue tester (Washinomiya Seisakusho, !) from 0 to 3 vs. at a cycle of about 6 seconds.

Also, unsaturated polyester waterproofing material (C) with dimension 10CII
IXIOCII, on an asbestos slate board 5 parts m thick
After 3 hours of painting, apply the above polyurethane coating waterproofing material (A) to a thickness of 21 m using a rubber spatula.
After curing at 0°C for 1168 hours, an abrasion test was conducted according to JIS K7204.

In addition, release silicone TSM65 is added to the polyester film.
0 (on Toshiba silicone), and then apply polyurethane waterproofing material (A) on top of it to a thickness of 3111+1. Three hours after painting, apply polyurethane waterproofing material (C) to a thickness of 21111+1 with a rubber spatula. Apply at 20°C, 168
After drying and curing for a period of time, it is removed from the polyester film, and a test piece is cut out using a circular rotary blade with an inner diameter of 28.7 on. During testing, two test pieces are placed one on top of the other and placed so that the striking end touches the polyurethane coating. JI impact resilience test
It was carried out according to SK6301.

Example-2 Diethylene glycol 11 was placed in a four-loaf flask equipped with a stirrer, a thermometer, a fractionator with a condenser, and a nitrogen inlet tube.
3.4 parts and 3.9 parts of maleic anhydride were added, and the temperature was 12.
After reacting at 0°C, 173.7 parts of cepatic acid and 13.0 parts of mesaconic acid were added and the esterification reaction was carried out at 210°C in a nitrogen stream, followed by 0.05 parts of hydroquinone.
A pale yellow liquid was obtained by dissolving 1 part in 268 parts of styrene. 10 parts of calcium carbonate and 5 parts of titanium white were uniformly mixed and dispersed in 100 parts of this pale yellow liquid at room temperature under high speed stirring. Immediately before use, 2.0 parts of benzoyl peroxide and 0.5 parts of paratoluidine were further blended to obtain an unsaturated polyester resin waterproofing material ([1]).

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

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

〔Effect of the invention〕

As is clear from the examples, when a waterproof layer made of polyurethane resin or polyester resin alone is applied to a wet surface, blisters and pinholes occur, and the physical properties are poor.

In contrast, the waterproof layer of the present invention does not have such drawbacks and is extremely suitable as a waterproof layer for roofs.

Claims (2)

[Claims] (1) A waterproof coating layer consisting of a lower layer made of a cured product of an unsaturated monomer and an unsaturated polyester resin, and an upper layer made of a polyurethane resin. (2) A patent claim characterized in that the unsaturated polyester resin contains 1 to 25 mol% of unsaturated acids at the terminals based on the total amount of dicarboxylic acids, and 8 mol% or less of unsaturated acids in the chains. The coating film waterproof layer according to item 1.