JPS599584B2 - Composition for waterproofing paint films - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition for waterproofing structures, and in particular to a waterproof coating that is flame retardant even when exposed to flame and can be used as an aesthetic finishing film for structures. A composition for waterproofing a coating that can form a film and can be used for both the interior and exterior of structures.

Water-permeable parts such as rooftops, walls, and floors of buildings must be treated with appropriate waterproofing, and methods traditionally used to waterproof these surfaces include asphalt waterproofing, sheet waterproofing, There are cement waterproofing methods, waterproofing methods using synthetic resin emulsions, etc., but the waterproofing method using synthetic resin emulsions has good workability, and the waterproof membrane formed can also have an aesthetic finish. Since the advantages are eliminated, it is also expected to be used for interior applications by taking advantage of this advantage.

However, coatings formed from synthetic resin emulsions are generally flammable, and systems in which ordinary optical fillers are added are also flammable, so they should not be used for interior applications where flammability is a problem. The current situation is that this is not possible. According to the Building Standards Act, at least J
It is necessary that the material is an IS class 3 flame retardant material or higher. Naturally, it is also preferable that the material be flame retardant for exterior use. It is well known that various halogen compounds, phosphorus compounds, antimony oxide, etc. are generally used alone or in combination to make synthetic resins flame retardant.

A flame-retardant composition can be obtained by adding these to a composition for waterproofing a paint film, but a paint film formed from a waterproofing material containing such a halogen compound emits a high amount of smoke when burned. Generally, when applying a coating over a large area, consideration must be given to hygiene, toxicity, etc. caused by spraying, and the use of these flame retardants is not preferred. The present invention Nagisa et al.
In view of this current situation, we have carefully investigated ways to impart flame retardancy to coating films formed by these methods without sacrificing the excellent advantages of coating film waterproofing methods using synthetic resin 1-mulsion. However, it was discovered that flame retardancy could be imparted by adding and mixing a specific inorganic light filler 2 yuzu to an aqueous solution of vinyl polymer, and there were no problems with hygiene or toxicity during the installation. The present inventors have discovered that it is possible to obtain a composition for waterproofing paint films that does not have any of the following problems and does not impair waterproofness, workability, aesthetics, etc., and has thus arrived at the present invention.

The gist of the present invention is to provide at least 10 parts by weight of aluminum hydroxide and 1 part by weight or more of dawsonite to 100 parts by weight of the solid content of the aqueous vinyl polymer liquid having a glass transition temperature of -25°C or less. The present invention provides a flame retardant composition for waterproofing paint films, which has a viscosity of 500 cps or more when 11 to 150 parts by weight of the above inorganic optical filler mixture and 0.1 to 50 parts by weight of short fibers are added.

It is important to always use aluminum hydroxide and dawsonite together during the filling used in the present invention.

Aluminum hydroxide is a component that undergoes an endothermic dehydration reaction when the waterproof coating film is burned, suppresses heat generation in the coating film, and imparts a flame retardant effect to the coating film.A waterproofing composition in which only aluminum hydroxide is added as a filler. has poor storage stability and poor workability during use, and is unable to impart stable flame retardancy to the resulting coating film. Also, Dawsonite is
Either natural or synthetic materials can be used, and in terms of chemical composition, NaAl(0H)2C03,
NaAl(0H)2C03・XH2O, Na2OAj2
It is represented by a white orthorhombic mineral represented by O3.2C02.2H20, and its morphology may be fibrous or other forms.

It is artificially synthesized using sodium aluminate as a starting material. When dawsonite is exposed to flame, it dehydrates and releases carbon gas, which is thought to exert a flame retardant effect.
A waterproofing material containing only dawsonite as a flame retardant is not preferred because its storage stability is insufficient and the coating film formed from this waterproofing material is prone to cracking. On the other hand, in the present invention, by using specific amounts of aluminum hydroxide and dawsonite, which cannot be used alone, J can be formed without reducing the storage stability of the waterproof coating composition. We have obtained a composition that not only provides excellent flame retardancy to the paint film, but also has the excellent workability, waterproofness, and aesthetic properties required of a composition for waterproofing paint films. .

The amount of aluminum hydroxide added is at least 10 parts by weight per 100 parts by weight of the solid content of the aqueous vinyl polymer solution.

If it is less than this, it will not be possible to obtain a waterproof composition that can provide the desired flame retardancy. Furthermore, the amount of Dawsonite added is at least 1 part by weight per 100 parts by weight of the solid content of the vinyl polymer aqueous solution; below this amount, a flame-retardant coating film cannot be formed from the waterproofing material containing Dawsonite itself. .

Furthermore, it is preferable to set the combined ratio of aluminum hydroxide/dawsonite to 30/1 to 2/1, as this exhibits particularly excellent flame retardancy and workability. Moreover, these aluminum hydroxide and dawsonite are not only hard-treated products, but also those subjected to various tank surface treatments are used.

In general, silane couplings that have been subjected to cutting, fatty acid treatment, etc. are also commercially available and can be used as they are. Specific examples of other inorganic fillers that can be used in the present invention include talc, mica, diatomaceous earth, acid clay, kaolin, quartz,
Iron powder, aluminum powder, flyash ultra white, white carbon, ferrite, litobone, titanium oxide,
Perlite, barite, zinc sulfate, zinc borate, zirconia, wood flour, pozzolan, carpon plaque, metal oxides such as calcium oxide, magnesium oxide, zinc oxide, barium oxide, lead oxide, aluminum oxide, etc., as well as calcium carbonate, carbonic acid Examples include magnesium, barium carbonate, strontium carbonate, magnesium hydroxide, and calcium hydroxide.

Waterproofing compositions containing these inorganic powder fillers promote the effect of preventing cracks and sagging of paint films formed from the compositions during film formation, and further improve waterproof properties and aesthetic appearance. can be done. The amount of these fillers added must be within 150 parts by weight of aluminum hydroxide and dawsonite per 100 parts by weight of the solid content of the vinyl polymer aqueous solution. . The coating film obtained from the composition added in excess of this value will have reduced adhesion to the base material, its elongation and elasticity will be reduced, and the structural crack followability of the structure will be reduced, resulting in a coating film with excellent waterproof properties. I can't. Further, specific examples of short fibers used in the present invention include natural or synthetic fibers in the form of powdered fibers, such as rock wool, glass wool, asbestos, polyvinyl chloride fiber, and polypropylene fiber. , vinylon fiber, nylon fiber. Fabrics such as fiber, polyester fiber, acrylic fiber, rayon, cotton, hemp, etc. can be used. These short fibers are added at a ratio of 0.1 to 50 parts by weight per 100 parts by weight of the solid content of the vinyl polymer aqueous solution. If it has a certain form, the amount added is set at a small value.

A coating film formed from a composition containing 0.1 to 50 parts by weight of these short fibers has improved strength and a beautiful pattern finishing effect. The added composition reduces painting workability, significantly impairs the ability to form beautiful patterns, and reduces the adhesion, flexibility, and crack followability of the coating film, forming a coating film with excellent waterproof properties. I won't be able to do that. The vinyl polymer used in the present invention must be water-soluble or water-dispersible, and must have a glass transition temperature of -25°C or lower.

When the glass transition temperature is -25°C or higher, the flexibility of the coating film formed from the waterproofing composition of the present invention becomes insufficient, and its adhesion also becomes insufficient. This is undesirable because it reduces the ability of the membrane to follow cracks and becomes a source of water leakage accidents. Specific examples of such vinyl polymers include A) at least one acrylic acid alkyl ester having an alkyl group having 2 to 10 carbon atoms;
B) 0.1 to 10% by weight of at least one α,β-monoethylenically unsaturated carboxylic acid, and at least one of other copolymerizable vinyl monomers.
Examples include polymers obtained by combining and copolymerizing tanks at a ratio of 49.9% by weight or less.

The aforementioned copolymer components (specific examples of 1Xi include alkyl groups such as ethyl group, n-propyl group, isopropyl group, n-propyl group,
-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-amyl group, isoamyl group, n-hexyl group,
Examples include acrylates such as cyclohexyl group, n-heptyl group, oxohebutyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, oxononyl group, n-decyl group, and oxodecyl group.

A composition containing a polymer containing 50% by weight or more of these copolymer components can form a coating film with good flexibility, adhesiveness, and elongation, and has excellent crack followability for structural cracks in structures. α, β- which are copolymerization components 03) of the above polymer
Specific examples of monoethylenically unsaturated carboxylic acids include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and itaconic acid monoalkyl esters, and these acid monomers are incorporated into the polymer. 0,1～
It is necessary to copolymerize in a proportion of 10% by weight.

These comonomers contribute to improving the dispersion stability of the copolymer used in the present invention in an aqueous medium, and have the effect of improving the affinity of inorganic fillers such as flame retardants and short fibers with the aqueous polymer. However, if too much of this component is polymerized, the alkali resistance, water resistance, etc. of the resulting coating will decrease So I don't like it. Specific examples of other copolymerizable vinyl monomers include acrylates other than component (1), alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, and dodecyl groups. , stearyl group, lauryl group, benzyl group, cyclohexyl group methacrylates, styrene,
Acrylonitrile, methacrylonitrile, vinyl chloride,
Vinyl propionate, acrylamide, methacrylamide, hydroxyalkyl acrylate or methacrylate, diacetone acrylamide, N-alkoxyalkyl acrylamide, dialkylaminoethyl acrylate, dialkylaminoethyl acrylamide, hydroxyalkyl acrylate or methacrylate, and vinylsiloxane. Also used are polyvinyl compounds such as polyacrylates of polyols. When a copolymer is prepared by selecting one of these monomers whose homopolymer has a high glass transition temperature as a copolymerization component, the strength of the copolymer, particularly at high temperatures, can be increased.

Among the above comonomers, monomers that serve as functional groups are 2
Copolymerization in a proportion of 5% by weight or less can improve the affinity with inorganic optical fillers such as aluminum hydroxide or improve the adhesion of the film to the substrate. The aqueous vinyl polymer liquid used in the present invention can be produced, for example, by combining the comonomers described above within the ranges described above and emulsion polymerizing the mixture in an aqueous medium containing an emulsifier.

The emulsifiers used in the emulsion polymerization method include anionic,
Or nonionic emulsified shaver is better.

To prepare the aqueous solution of the vinyl polymer used in the present invention, the emulsion may be used as it is or diluted with water as appropriate, but preferably the pH value is adjusted to 7 using ammonia, water-soluble amine potassium hydroxide, sodium hydroxide, etc. From the viewpoint of stability, it is preferable to adjust the acidic acid to 10 to 10, but even a slightly weakly acidic one can be used for optical analysis if it has good stability. The solid content of the aqueous vinyl polymer liquid used in the present invention is generally preferably in the range of 30 to 70% by weight. To prepare the waterproof composition of the present invention, a predetermined amount of aluminum hydroxide, dawsonite,
Other inorganic fillers and short fibers may be added, but in order to stabilize the viscosity of the resulting slurry,
Preferably, a dispersing agent in a proportion of 1 part by weight and an antifoaming agent in a proportion of 0.01 to 2 parts by weight are used together. In addition, examples of additives other than those mentioned above include Portland cement, alumina cement, blast furnace cement, and white cement.

The flame-retardant composition for waterproofing of the present invention forms a beautifully finished flame-retardant waterproof coating film by applying or spraying it on the roof or wall of a structure. In order to form a beautiful pattern without causing sagging or cracking of the coating film, the viscosity of the composition must be 500 cps or more, preferably in the range of 1,000 to 100,000 cps.

If the viscosity is too low, a sagging phenomenon occurs in the coating film, resulting in an unsatisfying coating film with an unsatisfactory appearance, and uneven thickness of the coating film is likely to occur, making it difficult to stabilize the flame retardant effect. To adjust the viscosity of the composition of the present invention, viscosity adjusting agents such as polyvinyl alcohol, polyacrylamide, polyethylene oxide, sodium alginate, carboxymethyl cellulose, hydroxyethyl cellulose and salts thereof, starch, water-soluble polyacrylic acid or Methacrylates 3 can be mentioned, and the amount of these viscosity adjusting additives is usually 3 parts by weight per 100 parts by weight of the polymer.
Preferably, the proportion is less than or equal to parts by weight.

In order to significantly improve the aesthetic properties of the coating film formed from the composition of the present invention, it is sufficient to add four dyes and pigments to the composition of the present invention.

When applying the composition of the present invention to a structure, a film thickness of 6 to 7 cm can be applied using a brush coating method, a roller coating method, a spray coating method, etc.
? The film thickness can be set appropriately depending on the purpose, but it is usually 0.5 to 371 cm.
It is about iR.

The material of the construction surface is not particularly limited, and concrete and mortar are the main materials, but other materials such as slate, iron, aluminum, and wood can also be used. The coating film coated with the composition of the present invention thus obtained exhibits excellent flame retardancy, has a good aesthetic appearance, has good adhesion to the base material, and has good waterproof properties and workability. shows. Its flame retardancy is higher than JIS Class 3 flame retardant material, and it can also be used as an interior material for structures.Compared to the conventional resin emulsion-based coating film waterproofing method, its application range is extremely wide and useful. It is. Example 1 The composition shown in Table 1 was mixed with 100 parts of deionized water, 1.25 parts of sodium dodecylbenzenesulfonate, 3.75 parts of polyoxyethylene nonyl phenyl ether, 0.54 parts of ammonium persulfate, Sodium hydrogen persulfate 0.39
After polymerizing at 70° C. for 6 hours, 10% aqueous ammonia was added to neutralize the mixture to obtain an aqueous polymer emulsion.

This polymer emulsion has a heating residue of 50% and a viscosity of 126.
cps. ．． The pH was 8.5, and the glass transition temperature of the polymer was -30°C.

For 100 parts of solid content of the obtained aqueous polymer emulsion, 60 parts of aluminum hydroxide, 16 parts of dawsonite,
A waterproofing composition having a viscosity of 32,000 cps was prepared by adding and mixing 81 parts of Stone 1i, 1 part of polyoxyethylene nonyl phenyl ether, 1 part of antifoam shavings, and 14 parts of water.

This waterproofing composition of the present invention has a size of 220 x 220 x 1
0 (1g1t) slate board to a thickness of about 1ig1t, and dried at room temperature. This product formed a coating film with an aesthetically pleasing pattern and was less tacky. This was subjected to a surface test for grade 3 flame retardancy based on JISA-1321 flame retardant test method for building interior materials and construction methods.

The results are shown in Table 2. Further, the composition of the present invention was poured onto a glass plate to a thickness of about 1 layer, dried, and the obtained film was peeled off from the glass plate and a tensile test piece was cut out. A tensile test was performed on this sample. The rice yield is also shown in Table 2.

As Comparative Example 1, 76 parts of calcium carbonate was used instead of the aluminum hydroxide dawsonite added to the waterproof composition of the present invention, and as Comparative Example 2, aluminum hydroxide was further added instead of dawsonite. 16
In Comparative Example 3, 6 parts of dawsonite was added in place of aluminum hydroxide in the above waterproof composition.
A coating film was formed by the same method using the same composition as the composition of the present invention, except that 0 part of the composition was added, and its performance was evaluated. The results are shown in Table 2. Second
As is clear from the results in the table, the composition of the present invention exhibits excellent flame retardancy, high elongation and strength, and exhibits excellent performance as a waterproof coating material.

On the other hand, even if a conventional optical filler as shown in Comparative Example 1 has excellent waterproof properties, it is flammable and cannot be used as an interior material. Furthermore, when flame retardation is achieved using only aluminum hydroxide as in Comparative Example 2, the storage stability of the slurry is poor and the coating film tends to sag. Further, in the case of Comparative Example 3, which is made only of dawsonite, the coating film tends to crack and does not exhibit waterproof properties. That is, when aluminum hydroxide and dawsonite are used together, as in the composition of the present invention, a composition exhibiting excellent flame retardancy and waterproof properties can only be obtained. In the JIS Al32l test, the conditions for JIS grade 3 are: smoke generation amount of CAl2O or less, temperature/time area of 350 or less, afterflame of 30 seconds or less, back crack width of 1/10 or less of the plate thickness, and no harmful deformation.

In addition, the tensile strength and elongation were measured using JISK-6 using Tampel No. 3 specimens.
It was measured in accordance with 301.

Example 2 Same aqueous polymer emulsion 100 as used in Example 1
1 part, aluminum hydroxide and dawsonite in the proportions shown in Table 3, and furthermore, 0.5 part of asbestos, 1 part of antifoaming agent, 1 part of polyoxyethylene nonyl phenyl ether, and 14 parts of water.
were added and mixed to obtain five waterproofing compositions.

Experiment numbers 1 to 4 show the waterproof composition of the present invention, and experiment number 5 is a comparative example. These waterproofing compositions were applied onto a slate board in exactly the same manner as in Example 1, and after drying,
A combustion test was conducted on JIS Al32L. The results are shown in Table 3. As is clear from Table 3, the composition of the present invention exhibited excellent flame retardancy and good workability.

On the other hand, Experiment No. 5, which is a comparative example, has exactly the same components as the composition of the present invention, but the total amount of dawsonite and aluminum hydroxide is outside the range of the present invention.
Although the coating film formed from such a composition is flame retardant, it cracks during combustion and does not meet the JIS Class 3 requirements, and its workability deteriorates and its adhesion to the base material deteriorates. It is not preferable because it has poor film formation properties. Example 3 100 parts by weight of the monomer composition shown in Table 4 were mixed with 1.25 parts by weight of sodium dodecylbenzenesulfonate, 3.75 parts by weight of polyoxyethylene nonyl phenyl ether, 0.54 parts by weight of ammonium persulfate, J A mixture of 0.39 parts by weight of sodium bisulfite and 100 parts by weight of deionized water was polymerized and neutralized in the same manner as in Example 1 to obtain a polymer emulsion having a glass transition temperature of -45°C.

To 100 parts of the obtained polymer emulsion, the proportions of aluminum trioxide dawsonite shown in Table 5, 0.5 part of asbestos, 0.1 part of pulp powder, 1 part of antifoaming agent, and polyoxyethylene nonyl 1 part of phenyl ether, 14 parts of water, and each inorganic filler shown in Table 5 were added in various proportions and mixed to obtain five types of waterproof compositions of the present invention.

When these were applied onto a slate board in the same manner as in Example 2, a coating film with good workability and excellent appearance was obtained.

Claims (1)

[Claims] 1(A) 50% by weight or more of an acrylic acid alkyl ester having an alkyl group having 2 to 10 carbon atoms, (B) α,β-
0.1 to 10% by weight of monoethylenically unsaturated carboxylic acid,
and (C) a polymer having a glass transition temperature of -25°C or less obtained by polymerizing a monomer mixture consisting of 49.9% by weight or less of at least one other copolymerizable vinyl monomer in an aqueous medium. 11 to 150 parts by weight of two or more inorganic fillers including at least 10 parts by weight of aluminum hydroxide, 1 part by weight or more of dawsonite, and 0.1 to 150 parts by weight of short fibers, based on 100 parts by weight of the solid content of the aqueous polymer solution. A composition for waterproofing a coating film of a construction having a viscosity of 500 cps or more when 50 parts by weight is added.