JPH06145446A - Frlame retardant composition having elasticity - Google Patents

Abstract

PURPOSE:To obtain a flame retardant composition, applicable to interior or exterior trim materials with a thickness equal to or larger than that of a substrate and having excellent flame retardancy and durability, etc., while holding the elasticity. CONSTITUTION:This flame retardant composition is obtained by adding 3-35 pts.wt. metallic salt of boric acid and 150-800 pts.wt. metallic hydroxide to 100 pts.wt. aqueous emulsion of a halogen-containing resin. The resultant composition is flame retarded by the synergistic action of a halogen with the metallic salt of the boric acid in the aqueous emulsion of the resin and the flame retarding is further promoted by dissociation and release of water of crystallization caused by heating of the metallic hydroxide. Excellent flame retardant effects can effectively be manifested without losing physical properties such as elasticity and weather resistance of the resin used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to interior and exterior paints for buildings,
The present invention relates to a flame-retardant composition having elasticity, which is useful as a base conditioning material, a protective finishing material for concrete surfaces, a metal anticorrosion protective material, and a repair paint for wallpaper.

[0002]

2. Description of the Related Art Conventionally, flame-retardant compositions of this kind have been used as elastic paints and coatings which can be applied to interior and exterior materials, wallpaper, etc. in a thickness of about 100 .mu. It is widely used as a fire protection material equivalent to base materials such as wood. And as such a conventional flame-retardant composition, the resin itself such as vinyl chloride / vinylidene chloride copolymer, vinyl chloride / vinyl acetate copolymer, vinylidene chloride / alkyl acrylate copolymer is flame-retardant. Vinyl chloride-based resins or vinylidene chloride-based resins are known. However, since such a flame-retardant composition relies on the flame-retardant property of the resin itself due to the high halogen content, adhesion to the adherend and film-forming property, flame-retardant property, weather resistance, thermal yellowing ,
Not only is the application naturally limited in terms of elasticity, but it was not always satisfactory in terms of flame retardancy and durability.

As a solution to the problems of the conventional flame-retardant composition, a flame-retardant composition in which a large amount of an inorganic flame retardant such as antimony trioxide or aluminum hydroxide is added to an aqueous resin emulsion is used. Flame-retardant composition in which an organic flame-retardant such as tetrabromobisphenol or chlorinated phosphate ester is added to the emulsion. Flame-retardant composition in which the amount of resin is reduced and a chlorine-containing binder is added. Addition-type flame-retardant compositions such as a flame-retardant composition to which a foamable substance is added have been proposed.

However, the flame-retardant composition to which the inorganic flame-retardant is added needs to contain a large amount of the flame-retardant, and therefore the content of the inorganic flame-retardant is inevitably contained in the coating film during use. It is extremely large, and is generally hard and brittle, making it difficult to obtain a flexible film. Further, since the flame-retardant composition to which the organic flame retardant is added uses a chlorine-based or bromine-based organic hydrophobic powder, miscibility with the organic binder, compatibility, dispersion stability However, there is a problem in that the separation of the flame retardant is likely to occur in some cases, and the performance of the coating film is likely to deteriorate. Therefore, a method of adding a water-soluble flame retardant is disclosed, but there is a drawback that the water resistance is significantly reduced, and similarly, in the case of adding an antimony-based flame retardant, in the treatment of a metal salt. Not only does it cause a problem, but since an expensive organic flame retardant is used, it is necessary to frequently use an inexpensive filler, and the resulting coating has the drawback of becoming hard. The flame-retardant composition to which the chlorine-containing binder of (1) is added needs to have a high chlorine content, so that not only the physical properties of the film and heat resistance are inferior, but also it is easy to color by light heat. There is. The flame-retardant composition to which the foamable substance is added is used in a very special way and is not common.

[0005]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the problems of the prior art, and it can be applied to an interior / exterior material with a thickness equal to or more than a material equivalent to a base material, and still retain elasticity. At the same time, it is intended to provide a flame-retardant composition having excellent flame retardancy and durability.

[0006]

That is, according to the present invention, 3 to 35 parts by weight of a metal salt of boric acid and 150 to 800 parts by weight of a metal hydroxide are added to 100 parts by weight of a halogen-containing resin aqueous emulsion. Is a flame-retardant composition having elasticity. The flame-retardant composition of the present invention is made flame-retardant by the synergistic action of the halogen contained in the resin aqueous emulsion and the metal salt of boric acid, and is difficult due to the dissociative release of water of crystallization accompanying the heating of the metal hydroxide. It further promotes combustion, and can effectively exhibit an excellent flame retardant effect without losing physical properties such as elasticity and weather resistance of the resin used.

The above-mentioned halogen-containing resin aqueous emulsion used in the present invention is from 12% by weight to 65% by weight based on the total amount of the additives.
% By weight, preferably 15% to 30%, 65% by weight
In the above cases, the heat resistance and weather resistance are inferior, and in the case of 12% by weight or less, the flame retardant effect tends to decrease. Further, for the purpose of imparting elasticity to the coating film, it is preferable to select the glass transition point of the emulsion resin at 5 ° C. or lower, and above 5 ° C., the elasticity of the coating film is likely to be impaired. The halogen-containing resin aqueous emulsion used in the present invention is an emulsion polymerization of a polymerizable unsaturated monomer containing a halogen atom such as chlorine or bromine in an aqueous medium, or an emulsion polymerization with another polymerizable unsaturated monomer. Generally, it can be produced by incorporating a flame retardant containing a halogen atom into the resin aqueous emulsion, if necessary. Examples of such a halogen-containing polymerizable unsaturated monomer include vinyl chloride, vinylidene chloride, mono- or di-chlorostyrene, bromostyrene, chloroprene, and any mixture thereof. If considered, vinyl chloride, vinylidene chloride and chlorostyrene are preferred. Further, in consideration of the purpose of use of the resin aqueous emulsion composition, it is desirable to copolymerize a halogen atom-containing unsaturated monomer with another polymerizable unsaturated monomer. Examples of the monomer include acrylic acid ester, methacrylic acid ester, vinyl acetate, ethylene and styrene.
Further, as the functional monomer, unsaturated carboxylic acid, hydroxyl group-containing monomer, amide group-containing monomer or the like may be used in combination. Further, as the flame retardant containing a halogen atom, for example, chlorinated phosphoric acid ester, chlorinated paraffin, hexabromocyclododecane, decabromodiphenyl oxide, hexabromobenzene, tetrabromoethane, pentadibromodiphenyl ether, dibromoethylbenzene. , Tetrabromobisphenol A,
Examples include tripromophenyl allyl ether, brominated polystyrene, and any mixture thereof. Also,
In order to produce an aqueous resin emulsion containing a flame retardant containing a halogen atom, a method of adding these flame retardants to the resin emulsion is usually used (Japanese Patent Laid-Open No. 2-265973 and Japanese Patent Laid-Open No. 4-13746). (See Japanese Patent Laid-Open No. 4-36359). In addition, as an aqueous resin emulsion containing such a flame retardant containing a halogen atom, "Acronal (registered trademark)" and "Diophane (registered trademark)" manufactured by Mitsubishi Petrochemical Bardish Co., Ltd., or Sumitomo Chemical Commercially available products such as "Sumikaflex (registered trademark)" and "Sumiace (registered trademark)" manufactured by Kogyo Co., Ltd. can be used. In such a halogen-containing resin aqueous emulsion, interparticle bonding progresses at the stage of evaporation of water, and a tough coating film rich in elasticity can be formed.

Examples of the metal salt of boric acid which exerts a synergistic action with halogen in the above resin aqueous emulsion include zinc borate, aluminum boride, iron boride, sodium borate, barium metaborate and the like.

The metal hydroxide as the flame retardant aid is
The amount of bound water per mol is 20% or more, and the decomposition temperature is 10
It is 0 ° C to 500 ° C, preferably 120 ° C to 450 ° C. When the decomposition temperature is 100 ° C or less, the dissociative release of crystal water accompanying heating is too fast, and when it is 500 ° C or higher, the dissociation of crystal water is dissociated. Release is too slow and both are unsuitable as flame retardant aids. Suitable metal oxides include, for example, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, dihydrate gypsum, dosonite, calcium aluminate and the like.

The flame-retardant composition of the present invention may contain a coloring material, clay, calcium carbonate, sericite, if necessary.
Inorganic substances such as borax and the like, and other non-halogen-based resin aqueous emulsions, film-forming aids, plasticizers, defoamers, dispersants, wetting agents, thickeners, emulsifiers and the like can be added. And, the blending of the flame-retardant composition of the present invention is preferably 100 parts by weight of the halogen-containing resin aqueous emulsion in solid content (however, 12% by weight with respect to the inorganic filler and the colorant).
The above), the metal salt of boric acid is 3 to 35 parts by weight,
The amount of the metal hydroxide is 150 to 800 parts by weight, the amount of the inorganic filler or the colorant is 0 to 300 parts by weight, and the amount of the other non-halogen resin aqueous emulsion is 0 to 50 parts by weight.

[0011]

EFFECTS OF THE INVENTION Since the present invention is constituted as described above, it is possible to make the flame retardant by the synergistic action of the halogen in the resin aqueous emulsion and the metal salt of boric acid, and to crystallize the metal hydroxide by heating. The dissociative release of water can further promote flame retardation, and an extremely excellent flame retardant effect can be effectively exhibited without losing the physical properties such as elasticity and weather resistance of the resin used.

[0012]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto.

Examples 1-6, Comparative Examples 1-8 Flame-retardant compositions were produced according to the formulation examples shown in Table 1.
The flame-retardant compositions obtained from Examples 1 to 6 and Comparative Examples 1 to 8 were tested for flame retardancy, bending, water resistance, and yellowing, and the results are shown in Table 2. . The test was conducted by the following method.

Flame-retardant performance test The flame-retardant performance is evaluated according to the following criteria by the surface test method of JIS A-1321. ◎ --- Equivalent to non-combustible judgment ○ --- Equivalent to quasi-non-combustible △ --- Equivalent to flame retardancy

Water Resistance Test Each of the product of the example and the product of the comparative example was applied onto an iron plate so that the dry film was 300 μm, and dried at 20 ° C. for 3 days. Then, after heat-treating this at 100 ° C. for 30 minutes,
It is immersed in warm water of 40 ° C. for 3 days and visually evaluated according to the following criteria. ○ ---- No abnormality △ ---- Finishing of film gloss x ---- Blisters

Yellowing Test A sample is prepared in the same manner as in the water resistance test, left at 60 ° C. for 100 hours, and the degree of yellowing of the film is visually evaluated according to the following criteria. ○ −−− Almost no discoloration × −−− Yellowing

Bending Test After preparing a sample in the same manner as in the water resistance test, the coated surface is placed outside and bent into a rod having a diameter of 10 mm. Then, the crack generation angle due to bending is evaluated according to the following criteria. ◎ --- 180 degrees ○ --- 120 degrees △ --- 90 degrees × --60 degrees

[0018]

[Table 1]

[0019]

[Table 2]

Claims (1)

[Claims] 1. A halogen-containing resin aqueous emulsion 100.
A flame-retardant composition having elasticity, which is obtained by adding 3 to 35 parts by weight of a boric acid metal salt and 150 to 800 parts by weight of a metal hydroxide.