JP2669011B2 - Flame retardant coating film waterproofing composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Object of the Invention <Industrial Application Field> The present invention has a polymer containing an alkyl acrylate or an alkyl methacrylate (hereinafter referred to as an alkyl (meth) acrylate), a polymer containing vinylidene chloride, and a compound having a triazine ring. The present invention relates to a composition for waterproofing a coating film, and relates to a composition for waterproofing a flame-retardant coating film characterized by a difference satisfying both waterproofing performance and flame retardancy. It has excellent characteristics as a surface coating material for the purpose of protective coating of objects and cosmetics, so it can be widely used in the field of civil engineering and construction.

<Prior art> In recent years, with the development of synthetic polymer chemistry for waterproofing structures, various polymers mainly composed of synthetic polymers, especially alkyl acrylate-based polymers having excellent weather resistance, have been used in aqueous media. A coating film waterproofing method using an aqueous dispersion dispersed therein, particularly an emulsion, has been actively performed.

The performance required for these coating film waterproofing agents is the ability to follow base cracks and the flexibility at low temperatures from the functional aspect of being used for waterproofing of buildings, and to prevent movement of structures and base cracks even in winter. Follows, does not cause sagging and decrease in strength even at high temperatures, has excellent non-stickiness and excellent gloss, and has excellent water resistance, chemical resistance, ultraviolet light resistance, and ozone resistance. Moreover, it is possible to walk on the coating film.

Conventionally, a polymer obtained by polymerizing an alkyl acrylate has been widely used as a coating film waterproofing agent, particularly in the form of an emulsion, so as to sufficiently satisfy the required performance.

However, in recent years, since the living environment has become overcrowded, there has been a strong demand for making materials used in all fields flame-retardant in respect of human life.

For example, to give examples of legal restrictions on the use of flame-retardant materials, non-combustible materials, semi-combustible materials and flame-retardant materials may be used in places where a large number of people enter and exit, such as theaters, public halls, hospitals and department stores. It is established by the Building Standards Law,
Also for paints, fire protection material certification number for construction No. 0003, 00
Part 04 and 0005 etc. have come to require some flame retardancy.

Currently, there are no special restrictions on flame retardancy for waterproof coatings, but especially in facilities that handle hazardous materials, the notification of dangerous materials under the Fire Service Act `` Urethane foam as a heat retaining agent for outdoor storage tanks is difficult. It has become desirable to pass the flame retardancy test in "About the criteria for judgment of flammability", and this tendency is expected to become stronger in the future.

However, most of the conventional coating film waterproofing agents are flammable.

Therefore, it is naturally necessary to make the coating film waterproofing agent flame-retardant, and various methods have been investigated for the purpose of flame-retarding.

The main methods thereof include a method of adding a flame retardant, a method of adding a nonflammable inorganic filler, a method of making the polymer itself flame retardant, and the like.

For example, as a method of adding a flame retardant, halogen phosphorus compounds such as perchloropentacyclodecane, tris (chloromonopropyl) phosphate, hexabromobenzene, tris (chlorobromopropyl) phosphate, which are known as flame retardants, and flame retardants are known. In this method, antimony trioxide, dicumyl peroxide, etc. are used as a combustion aid.

However, the method using these is not a preferable method because the flame retardant escapes with time, the strength and gloss of the obtained coating film decrease, and the cost increases.

As a method of adding the non-combustible inorganic filler, there is a method of blending inorganic fillers such as various metal oxides and hydroxides such as calcium and silica which can be obtained at a low cost. However, most of these inorganic substances have no effect unless incorporated in a large amount, and the main purpose is to suppress the amount of smoke generated, and the flame retardancy itself is weak. Furthermore, since the obtained coating film contains a large amount of the above-mentioned inorganic substances, its use is limited in that the original mechanical properties of the resin are significantly impaired, and it is difficult to satisfy both waterproof performance and flame retardancy. Is.

The method of making the polymer itself flame-retardant is to make the flame-retardant polymer by replacing the flammable polymer with a more flame-retardant polymer. It is carried out by changing the olefin-based or styrene-based polymer into a phenol resin, a polycarbonate, a nitrogen-containing polymer or a halogen-containing polymer.

However, the polymer obtained by the above method is poor in flexibility, and is used in applications where high elongation performance is required, such as flexibility at low temperatures and followability to cracks in the substrate, such as a coating film waterproofing agent. I couldn't use it.

That is, a coating film waterproofing agent satisfying both waterproofing properties and flame retardancy has not been known at all.

<Problems to be Solved by the Invention> The present inventors have demanded a coating film waterproofing agent that can satisfy both waterproofing performance and flame retardancy, which could not be solved by the above-mentioned conventional technology, especially as a coating film waterproofing agent. As a material that sufficiently satisfies the performance, an alkyl acrylate polymer, which has been widely used as a coating film waterproofing agent in the form of an emulsion, retains the performance as a coating film waterproofing agent while maintaining the performance as a coating film waterproofing agent. Various studies were conducted with the object of imparting flammability.

B) Constitution of the Invention <Means for Solving the Problems> The present inventors have conducted various studies to solve the above problems, and as a result, a specific monomer component, that is, an alkyl (meth) acrylate ester / Polymer having vinylidene chloride as a constituent monomer (hereinafter referred to as synthetic resin) A coating film waterproofing composition having a triazine ring is excellent in weather resistance, strength, flexibility, water resistance, flame retardancy, and the like. It was found to sufficiently follow the deformation, and it was found to be a coating film waterproofing composition having extremely excellent waterproof performance and flame retardant performance,
The present invention has been completed.

That is, the present invention relates to a polymer containing at least one alkyl (meth) acrylate having an alkyl group having 4 to 10 carbon atoms and vinylidene chloride in the same structure as constituent monomers, or a different structure. A mixture of two or more polymers containing each of the above monomers separately or together, wherein the vinylidene chloride content is 10% of the total monomers.
The invention relates to a flame-retardant coating film waterproofing composition, which is an aqueous dispersion of a compound having a triazine ring in an amount of ˜60% by weight.

-Synthetic resin In the present invention, a polymer containing at least one kind of alkyl (meth) acrylic acid having an alkyl group having 4 to 10 carbon atoms and vinylidene chloride as constituent monomers in the same structure, Or a mixture of two or more polymers containing each of the monomers separately or together in different structures, wherein the content of vinylidene chloride is 10 to 10
What is 60% by weight is used as a synthetic resin, and a method for obtaining it is as follows.

(1) Copolymerization of an alkyl (meth) acrylate and vinylidene chloride or their monomers and other monomers in an aqueous medium.

(2) A mixture of a polymer obtained by polymerizing a monomer containing an alkyl (meth) acrylate and a polymer obtained by polymerizing a monomer containing vinylidene chloride.

The synthetic resin used in the present invention essentially comprises, as monomers constituting it, at least one kind of alkyl (meth) acrylate having an alkyl group having 4 to 10 carbon atoms and vinylidene chloride, The composition ratio is as follows.

That is, vinylidene chloride accounts for 10 to 60% by weight, preferably 15 to 40% by weight, of all monomers. If the proportion of vinylidene chloride is less than 10% by weight, it is difficult to provide sufficient flame retardancy, and if it exceeds 60% by weight, the flexibility and weather resistance of the coating film become inferior, and sufficient waterproof performance is obtained. Becomes difficult.

Further, it is preferable that the total amount of the alkyl (meth) acrylate and vinylidene chloride is 80% by weight or more based on the total amount of all the other monomers used as desired. When the amount is less than 80% by weight, the flexibility and weather resistance of the coating film are poor and it becomes difficult to obtain sufficient waterproof performance, which is not preferable.

Specific examples of the alkyl (meth) acrylate having an alkyl group having 4 to 10 carbon atoms include acrylic acid having an alkyl group such as butyl, isobutyl, 2-ethylhexyl, n-octyl, and n-hexyl, or Mention may be made of esters of methacrylic acid.

According to the present invention, an ester having an alkyl group having a carbon number of less than 4 has a single alkali for solving the above-mentioned problems in terms of alkali resistance, and an ester having an alkyl group having a carbon number of more than 10 has a low cold resistance. It cannot be used as a monomer, that is, an essential monomer constituting the synthetic resin of the present invention.

As a simple substance constituting the synthetic resin of the present invention, in addition to the above-mentioned alkyl (meth) acrylate and vinylidene chloride, various other copolymer monomers can also be used. Examples thereof include acrylic acid, methacrylic acid, acrylonitrile, ethylene, vinyl acetate, vinyl chloride, styrene, butadiene, (meth) acrylic acid alkyl ester other than the above (meth) acrylic acid alkyl ester, itaconic acid, maleic acid, Examples thereof include crotonic acid. Above all, acrylic acid, methacrylic acid and acrylonitrile are often used in combination in appropriate amounts to help improve the stability and mechanical properties of the emulsion, and are preferred as monomers to be used in combination.

As the synthetic resin used in the present invention, those in an emulsion state obtained by polymerizing the monomer by a conventional method using a commonly known emulsifier, from the viewpoint of stability when used as an aqueous dispersion. Also, it is preferable from the viewpoint of being easily obtained. As an emulsion, the usual solid content concentration is 30 ~
70% is fine. Furthermore, the pH value of the emulsion is 5
From the viewpoint of stability, it is preferably from 9 to 9 in which the pH value of the emulsion is adjusted using an aqueous ammonium solution, an amine, sodium hydroxide, potassium hydroxide or the like. However, even an emulsion in the acidic region having a pH value of 5 or less can be sufficiently used for achieving the object of the present invention as long as the emulsion has good stability.

The compound having a triazine ring, which is another component of the composition for waterproofing a flame-retardant coating film in the present invention, has an effect of improving the flame retardancy of the waterproof coating film, and also acts as an extender. It is preferable to add 2 to 100 parts by weight to 100 parts by weight of the synthetic resin, and more preferably 2 to 40 parts by weight. If the amount is less than 2 parts by weight, it is difficult to provide the effect of imparting flame retardancy. If the amount is more than 100 parts by weight, the flexibility and strength of the coating film tend to be impaired, and thus it is desirable to avoid it.

Here, as the compound having a triazine ring, melamine and its derivatives and polymers thereof can be mentioned as preferable compounds.

The melamine derivative means a compound in which the amino group of melamine is substituted, and specific examples include methylolmelamine and melamine cyanurate.

Specific examples of polymers of melamine and its derivatives include melamine / (aceto or benzo) guanamine / phenol, cresol or dimethylphenol / formaldehyde polycondensate, and melamine / (aceto, benzo or form) guanamine / formaldehyde / alkyl. Monoalcohol (C ₁ -C ₁₂ ) polycondensate, melamine / (aceto,
Benzo or form) guanamine / formaldehyde polycondensate, melamine amino resin, melamine / alkyl (C ₁₀
-C ₂₀₎ glycidyl ether / formaldehyde polycondensate, melamine / ethyleneurea / formaldehyde / methanol polycondensate, melamine peroxide addition compounds, melamine / guanidine / formaldehyde polycondensate, melamine / p- toluenesulfonamide / formaldehyde / Alkyl monoalcohol (C ₁ -C ₁₂ ) polycondensate, melamine / paratoluene sulfonamide / formaldehyde polycondensate, melamine / (phenyl, benzol or tolyl) sulfonamide / formaldehyde polycondensate, melamine /
Phenol, cresol or dimethylphenol / formaldehyde polycondensate, melamine / phenol / p-toluenesulfonamide / formaldehyde polycondensate, melamine / hexamethylenetetramine / formaldehyde polycondensate, melamine / benzoguanamine / poly (10-40)
Oxyalkylene (C ₂ -C ₂₎ polyols or poly (2
10) Ester polyol Adipate / Butanediol and tolylene diisocyanate / hexamethylene diisocyanate / xylylene diisocyanate / reaction product of monoethanolamine and urea / formaldehyde polycondensate, melamine / formaldehyde / alkyl (C ₂ ~
C ₁₇ ) Carboxylic amide / methanol polycondensate, melamine / formaldehyde / alkyl (C ₁ -C ₁₂ ) monoalcohol / alkyl (C ₂ -C ₁₀ ) polyhydric (2-4) alcohol polycondensate, melamine / formaldehyde / alkyl monoalcohol (C ₁ ~C ₁₂₎ polycondensates, melamine / formaldehyde / alkylene (C ₂ ~C ₁₂₎ glycol polycondensate, melamine / formaldehyde / alkylene (C ₁₀ -C
₁₅ ) Foli (2-4) all / alkylene (C ₁ -C ₃ ) poly (1-3) amine polycondensate, dicyandiamine modified product of melamine / formaldehyde polycondensate, melamine / formaldehyde condensate, melamine / A polycondensate of formaldehyde / sulfonic acid light metal salt (sodium, potassium, magnesium, calcium), a melamine / formaldehyde / methanol polycondensate, a melamine / lignin / formaldehyde polycondensate, and the like.

In the present invention, melamine is most preferably used, and melamine significantly improves flame retardancy by adding a relatively small amount, and furthermore, the specific gravity, color tone, and mechanical properties of the obtained resin composition, for example, tensile strength. It is excellent in that it does not impair the critical elongation and the like, reduces the stickiness of the coating film, and is inexpensive in price.

Further, when a known inorganic flame retardant auxiliary is used in combination with the composition of the present invention, the flame retardancy can be further improved, and among the inorganic flame retardant auxiliary, antimony trioxide is preferable. The inorganic flame-retardant auxiliary is used in an amount of 30 parts by weight or less, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the synthetic resin. If the amount is more than 30 parts by weight, not only the effect corresponding thereto is not observed, but also the water resistance of the coating film is lowered, which is not preferable.

In particular, for applications requiring flexibility at low temperatures and a high degree of flame retardancy, the composition for waterproofing a flame-retardant coating film according to the present invention may be provided with an inorganic flame-retardant auxiliary such as antimony trioxide. It is preferable to use an agent together.

Further, in order to further improve the flame retardancy of the composition having improved flame retardancy by using an inorganic flame retardant auxiliary such as antimony trioxide in combination, it is preferable to further use a zinc compound in combination, and it is preferable as the zinc compound. The one is zinc oxide.
It is preferable to add the phosphite compound in an amount of 30 parts by weight or less, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the synthetic resin. Even if the amount exceeds 30 parts by weight, no corresponding effect is observed.

In addition to the effect of improving the flame retardancy, the combined use of the above zinc compound has a carboxyl group derived from an optionally copolymerized monomer other than the alkyl (meth) acrylate and vinylidene chloride, and (meta). ) The toughness is imparted to the coating film by salt-forming crosslinking between a carboxyl group or the like generated by saponification of an alkyl acrylate and zinc ions generated by dissociation of a zinc compound in water,
Further, it also has an effect of reducing stickiness of the coating film, and in particular, an effect of controlling the balance between physical properties of the coating film and flame retardancy. In particular, when zinc oxide is used, the composition for waterproofing a flame-retardant coating film of the present invention does not make the pH highly alkaline, and the obtained coating film shows a sufficient salt-forming crosslinking effect, and further has a color tone. Particularly excellent effects such as excellent yellowing can be obtained.

In order to further improve the flame retardancy of the composition for waterproofing a flame-retardant coating film in the present invention, generally known flame retardants, various metal oxides including calcium and silica which can be obtained at low cost, and water. It is of course possible to incorporate an inorganic filler such as an oxide into the composition of the present invention.

However, most of these flame retardants and inorganic substances have no effect unless incorporated in large amounts, and the resulting coating film contains a large amount of the above flame retardants and inorganic substances. There is a limit to use in that it significantly impairs
It is preferably 100 parts by weight or less with respect to parts by weight.

If necessary, a plasticizer may be used in combination with the coating film waterproofing composition of the present invention, but in this case, not only the mechanical properties of the coating film are impaired when used in a large amount, but also the aesthetics of the coating film are impaired by the bleeding of the plasticizer. Since it induces unfavorable properties, etc., use should be avoided as much as possible, and it is preferable to keep 10 parts by weight per 100 parts by weight of the synthetic resin,
More preferably, it is 5 parts by weight or less.

The plasticizer used is not particularly limited, but it is more preferable to appropriately select and use a plasticizer that imparts flame retardancy and has little bleeding.

Examples of the plasticizer capable of imparting flame retardancy include tris (chloroethyl) phosphate, tris (2-chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (2-chloropropyl) phosphate, ethylenebis (bischloroethyl). Phosphate), bis (chloropropyl) monooctyl phosphate, polyoxyethylene bis (bischloroethyl phosphate), 2,2, -bis (chlorochloromethyl) propylene bis (bischloroethyl phosphate), chloroethyl phosphate Chlorinated phosphates such as fate oligomers, bis (2,3, -dibromopropyl) 2,3, -dichloropropyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, Phenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, there are phosphoric acid esters, such as carboxymethyl les sulfonyl diphenyl phosphate.

Incidentally, it is naturally possible to use a plasticizer having no flame retardancy-imparting effect within a range not departing from the spirit of the present invention.

In addition, it is also possible to add an ultraviolet absorber to the composition for waterproofing a flame-retardant membrane of the present invention. Examples of the ultraviolet absorber used include phenyl salicylate, 4-t-butylphenyl salicylate and p-octylphenyl. Cysilate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5-chloro-2-hydroxybenzophenone, substituted acrylonitrile and the like.

If necessary, the composition for waterproofing a flame-retardant coating film of the present invention can contain a bone aggregate, a single fiber, a surfactant, a viscosity stabilizer, an antifoaming agent and the like as required.

Examples of bone agents include talc, mica, acid clay,
Diatomaceous earth, kaolin, quartz, iron powder, fly ash, titanium white, lithopone, baryta, wood powder, zirconia,
Perlite, vermiculite, shirasu balloon, carbon black, and holly carbon are used.

The addition amount is preferably 1000 parts by weight or less, more preferably 10 to 100 parts by weight, based on 100 parts by weight of the synthetic resin. If the aggregate is added in an amount of 1000 parts by weight or more, the flexibility of the coating film is lost, and it becomes difficult to exhibit sufficient waterproofing performance.

Further, as the single fiber, an inorganic fibrous material, a natural fiber or a synthetic fiber can be used, and specific examples include asbestos, rock wool, glass wool, skugo wool, pulp, polyethylene fiber, polyvinyl chloride fiber, vinylon fiber, nylon. Fibers, acrylic fibers, polyester fibers, cotton, hemp, etc. are used.

The amount of addition is preferably 50 parts by weight or less, more preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the synthetic resin. It is not preferable because it is poor in sex.

Surfactants are used to improve the dispersibility of aggregates. Examples of such surfactants include ethers such as alkyl or alkylphenol of polyoxyethene and sorbitan fatty acids of polyoxyethylene. And ester such as oxyethylene-oxypropylene block polymer.

Such a surfactant is 0.0 to 100 parts by weight of the synthetic resin.
It is preferable to add about 5 to 5 parts by weight. If the amount is small, it is difficult to stably mix the aggregate, and if the amount is large, the toughness of the coating film tends to decrease.

As the viscosity stabilizer, for example, lignin sulfonic acid,
Soda, potassium, ammonium salts, and the like such as polyacrylic acid, polymethacrylic acid, and tripolyphosphoric acid are used, and the compounding amount is preferably about 0.1 to 5 parts by weight based on 100 parts by weight of the synthetic resin. If the blending amount is small, the effect as a viscosity stabilizer is not exhibited, and if the blending amount is large, the water resistance of the coating film tends to be poor.

Further, as the defoaming agent, there are octyl alcohol, cabryl alcohol, lauryl alcohol, cyclohexanol and the like, and the compounding amount thereof is 100 parts by weight of the synthetic resin,
About 0.005 to 0.2 parts by weight is preferable.

The composition for waterproofing a flame-retardant coating film according to the present invention is applied or sprayed on the surface of a structure to be waterproofed to form a coating film. The viscosity of the composition is 300 cps or more (B-type viscometer: 30 rp.
m, rotor No. 2, 20 ° C.), and more preferably about 1000 to 50000 cps.

If the viscosity is less than 300 cps, the leveling property will be too high,
It becomes difficult to apply thick coating at once, and in the case of high viscosity, there is an advantage that thick coating can be applied, but when it is too high viscosity,
Difficulty in coatability tends to occur.

Further, the coating film waterproofing composition of the present invention can be freely colored, and as the colorant, ordinary dyes and pigments are used.

When applying the composition of the present invention, it is preferable to apply the composition so as to have a thickness of 100 μ or more, preferably 300 to 3000 μ. If the film thickness is too thin, the ability to follow the base cracks, etc. will decrease and cause water leakage.If the film thickness is increased, the ability to follow the above will be improved and cracks and cracks will disappear, but if it is too thick, it will also cope with it. No improvement in the effect achieved is observed.

It is also possible to apply the undercoating agent to the body in advance and then apply the flame retardant coating film waterproofing composition of the present invention.

Examples of the surface treatment agent include epoxy resin emulsion, general commercially available emulsion type or solvent type paint, and adhesive.

Further, when using the flame-retardant coating film waterproofing composition of the present invention,
For large areas of joints and gaps of structures that are to be waterproofed, the voids are previously filled with a cement mixture mixed with a sealing agent, mortar and synthetic resin emulsion, and then used for waterproofing of the present invention. It is also preferred to apply the composition.

In addition, an acrylic resin or an acrylethane resin can be treated on the coating film waterproofing composition of the present invention for the purpose of protecting the coating film and providing good appearance. However, the flame retardancy is impaired if the coating amount is increased, so that the coating thickness is preferably 300 μm or less.

The object to which the composition for waterproofing a flame-retardant coating film of the present invention can be applied is a general civil engineering structure, for example, concrete, mortar, a lightening agent such as an ALC plate or a plaster board, and a metal such as an iron plate or aluminum. It can be used for parts made of wood, veneer and other materials.

<Action> It is known that melamine resin is flame-retardant, and there is an example in which melamine itself is tested as a flame retardant. However, in an aqueous dispersion, a compound having a specific synthetic resin and a triazine ring is particularly preferred. It is not known at all that the aqueous dispersion used in combination produces an effect as an excellent flame-retardant coating film waterproofing composition, and the present inventors have found it for the first time. is there. Although it is unclear by what action this effect is exerted, it is only exhibited when a polymer containing an alkyl (meth) acrylate and vinylidene chloride and a compound having a triazine ring are used in combination.

Further, the compound having a triazine ring is a water-dispersed film-forming composition composed of a polymer containing vinylidene chloride as a constituent monomer, and usually has, over time due to dehydrochlorination derived from vinylidene chloride units. Is considered to be eliminated by the chloride ion scavenging action of the triazine ring.However, the composition of the present invention comprising a polymer containing vinylidene chloride as a constituent monomer has stability over time. And an excellent effect of producing a unique effect contrary to conventional knowledge.

<Examples> Hereinafter, the flame-retardant coating film waterproofing composition of the present invention will be described more specifically with reference to Examples and Comparative Examples.

 The present invention is not limited to the embodiments.

 The tests in Examples and Comparative Examples are as follows.

 The coating film used in the test had a thickness of 1 ± 0.2 mm.

(1) Coating physical properties Untreated 20 ° C. tensile test was performed in accordance with JIS-A-6021 “Test of acrylic rubber roof waterproof coating agent”.

(2) Weather resistance In accordance with JIS-A-6910, the appearance of the coating film after 1000 hours of ultraviolet treatment with JIS-A-1415 was visually observed.

(3) Flame Retardancy The fire time and the combustion length were measured based on the test of the Fire Service Law Dangerous Goods Related Criteria "Judgment Criteria for Urethane Foam as Heat Insulating Agent for Outdoor Storage Tanks". The determination of good or bad of the low viscosity was made when the burning time was 120 sec or less and the burning length was 60 mm or less.

(4) Film-forming property The film-forming state 24 hours after application of the composition for preventing a flame-retardant coating film was visually observed.

Example 1 The composition of A shown in Table 1 described below was reacted at 62 ° C. for 9 hours, and the pH was adjusted to 7.5 by adding aqueous ammonia to prepare an aqueous polymer dispersion A.

Next, according to the composition of Example 1 shown in Table 2 below,
100 parts by weight of an aqueous dispersion (solid content) of polymer A, 2 parts by weight of pulp, 23 parts by weight of melamine, 10 parts by weight of calcium carbonate, 4 parts by weight of titanium oxide, 10 parts by weight of antimony trioxide, a dispersant (polyacrylic acid) Soda) 1 part by weight, thickener (polyacrylic acid) 2 parts by weight, antifoaming agent (Nika Kagaku Co., Ltd .: EP-3)
0) 0.2 parts by weight were uniformly mixed to prepare a non-viscous coating film waterproofing agent slurry. The viscosity of this product was 18000 cps.

The obtained flame retardant coating film waterproofing agent slurry was tested for each item in accordance with the above-mentioned test method. As shown in Table 2, the coating film properties, flame retardant, flame retardancy, weather resistance, film formation All of the sexes showed good results.

Also, using this coating film waterproofing agent slurry, an alkali resistance test and a cold resistance test were conducted. The alkali resistance test is
According to JIS A6021, the coating film was immersed for 7 days in an aqueous solution of saturated calcium hydroxide in a 0.1% by weight aqueous sodium hydroxide solution, and the elongation was measured. The cold resistance test is also JIS A
According to 6021, the elongation between the grips of the coating film at −20 ° C. was measured. As a result, the elongation after the alkali resistance test was
422%, the elongation after cold resistance test is 70%,
All showed good results.

Examples 2-3 In accordance with the method of Example 1, after preparing aqueous dispersions B and C of the polymers shown in Table 1, the flame-retardant paint film waterproofing of Examples 2 and 3 of Table 2 was carried out. An agent slurry was prepared and each test was performed.

As for the results, as shown in Table 2, all showed good results. As shown in this example, when a synthetic resin having a high vinylidene chloride content is used, sufficient flame retardancy can be obtained even if the amount of melamine used is reduced.

Example 4 In accordance with the method of Example 1, a flame-retardant coating film waterproofing agent slurry of Example 4 of Table 2 was prepared using the water-acid solution A of the polymer described in Table 1, and The test was conducted.

 The results showed good results, as shown in Table-2.

In particular, as compared with Example 1, it can be seen that the coating film becomes tough due to the salt-forming crosslinking effect of zinc oxide, and the flame retardancy is greatly improved.

Example 5 According to the method of Example 1, after preparing aqueous dispersions E and F of the polymers described in Table 1, a flame-retardant coating film waterproofing agent slurry of Example 5 in Table 2 was prepared. Then, each test was carried out.

 The results showed good results, as shown in Table-2.

As is apparent from the results, the synthetic resin having a monomer composition unsuitable as the flame-retardant coating film waterproofing composition of the present invention, that is, the polymer aqueous dispersion F does not contain vinylidene chloride. By adjusting the content of vinylidene chloride in the synthetic resin in the aqueous dispersion by blending the aqueous dispersion E of the polymer containing vinylidene (in the synthetic resin by blending the aqueous dispersion E and F of the polymer) The content of vinylidene chloride is 18 parts by weight with respect to 100 parts by weight of the whole resin, which is equivalent to that of the dispersion A), indicating that the composition for waterproofing a flame-retardant coating film can exhibit sufficient performance.

 This shows the wide versatility of the present invention.

Comparative Examples 1-2 According to the method of Example 1, the coating film waterproofing agent slurries of Comparative Examples 1 and 2 of Table 2 were prepared using the aqueous dispersions A and B of the polymers shown in Table 1. , Each test was conducted.

As a result, as shown in Table-2, the composition other than the composition of the present invention is not excellent as the waterproof film waterproofing agent having flame retardancy. That is, those containing no vinylidene chloride, such as Comparative Example 2, are extremely inferior in flame retardancy even when melamine is used. Further, as seen in Comparative Example 1,
Even when the same synthetic resin as in Example 1 is used, when aluminum hydroxide, which is generally preferred as a flame retardant, is mainly used, the flame retardancy is hardly improved as compared with Example 1.

Comparative Example 3 In the composition of A in Table 1, except that 2-ethylhexyl acrylate was changed to ethyl acrylate, an aqueous dispersion A ′ of a polymer was prepared according to the method of Example 1 with the same composition as A. Prepared. Thereafter, a flame-retardant coating film waterproofing agent slurry having the same composition as that of Example 1 in Table 2 was prepared, and each test was performed.

The results, as shown in Table 3, are excellent in flame retardancy, weather resistance and film formability, but very poor in alkali resistance and cold resistance.

Comparative Example 4 An aqueous dispersion A of a polymer was prepared in the same manner as in Example 1, except that 2-ethylhexyl acrylate was changed to dodecyl acrylate in the composition of A in Table 1. After that, a flame-retardant coating film waterproof slurry having the same composition as in Example 1 in Table 2 was prepared and each test was carried out.

The results, as shown in Table-3, are excellent in flame retardancy, weather resistance and film formability, but poor in alkali resistance and very poor in cold resistance.

C. Effects of the Invention The composition of the present invention is a composition for waterproofing a coating film having excellent waterproofness and flame retardancy, and is used in theaters, public halls, hospitals, department stores, and the like, which are subject to legal restrictions on the use of flame retardant materials. It is widely used as a waterproof film for buildings, or as a waterproof film for facilities that handle hazardous materials that may be regulated by the Fire Service Act, and can contribute to the prevention of human loss due to fire. The effect is that it is a great contribution to the civil engineering and construction industry.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C09D 133/06 PGF C09D 133/06 PGF (56) References JP-A-61-166808 (JP, A ) JP-A-2-64176 (JP, A) JP-B-50-10344 (JP, B1)

Claims (1)

(57) [Claims] 1. A polymer containing at least one alkyl acrylate or alkyl methacrylate having an alkyl group having 4 to 10 carbon atoms and vinylidene chloride in the same structure as constituent monomers or different polymers. A mixture of two or more polymers containing each of the monomers separately or together in the structure, wherein the content of vinylidene chloride is 10 to 60% by weight of all monomers; And a water-soluble dispersion of a compound having a triazine ring.