JPS60212474A - Flame-retardant asphalt-based hotmelt composition - Google Patents

Abstract

PURPOSE:To provide the titled composition having extremely high flame-retardance and excellent water-resistance, freezle-resistance and adhesivity, available at a low cost, and useful as a roofing material, etc., by adding a flame- retarding assistant containing antimony or boron to a specific asphalt-based hotmelt composition. CONSTITUTION:The objective composition can be produced by mixing (A) 100pts. (wt.) of an asphalt-based hotmelt containing asphalt as a component with (B) 5-50pts. of at least one kind of ammonium halide powder having an average particle diameter of <=30mum (preferably powder surface-treated with an organic material, especially with a surfactant) and (C) 0-10pts. of (i) an antimony-based flame-retarding assistant (e.g. antimony trioxide) and/or (ii) a boron-based flame- retarding assistant (e.g. zinc borate), e.g. under melting.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to compositions, and more particularly to flame-retardant asphalt-based hot melt compositions that have extremely high flame retardance and are inexpensive.

Currently, asphalt-based hot melt is waterproof.

It is widely used because it has excellent physical properties such as cold resistance and adhesiveness, and its greatest advantage is that it is particularly inexpensive. The main fields of application are protective coatings for underground steel pipes and roofing materials. Examples include bonding materials for various building materials, low-temperature warehouses, and refrigerator parts.

On the other hand, combustible materials such as fibers, plastics, and building materials made from petroleum products are treated with general chemicals.

In addition to the balance of physical properties, safety against flames, that is, flame retardancy, is strongly required.Currently, it is said that the provision of flame retardancy determines the possibility of expanding the use of the material. It's not too much to say. Naturally, asphalt-based hot melts made from petroleum products are in a similar situation, and there is a strong demand for flame retardant properties.

Various studies have been conducted on flame retardant asphalt-based hot melts, as seen in the literature [Polymer no Tomo, April issue, 1981, pages 219-226, title (Flame retardant asphalt)]. Currently, it is common to add aluminum hydroxide and/or chlorinated paraffin to the hot melt to impart flame retardancy. However, since the flame retardant function of aluminum hydroxide is small, in order to obtain the desired flame retardancy, it is generally necessary to
It must be added in an amount of 0 parts by weight or more.

As a result, there is a problem in that the inherent physical properties of the hot melt, particularly the tackiness, inevitably deteriorate. On the other hand, although chlorinated paraffin has a great flame retardant function, it is subject to high temperatures (140 to 180°C) and shear stress when preparing chlorinated paraffin by adding it to the hot melt.
Chlorinated paraffin has the problem of decomposing and producing hydrogen chloride, which is toxic and corrosive to equipment. Therefore, there is an urgent need in the hot melt industry to develop a flame retardant that eliminates the above-mentioned problems.

The present inventors aimed to develop an excellent flame-retardant asphalt-based hot melt composition that could solve the above-mentioned problems, and as a result of intensive studies, they found that it has extremely high flame retardancy, and furthermore, asphalt-based hot melt composition. The present invention has been completed, which has the advantage that the original physical properties of the hot melt are hardly impaired because the amount of flame retardant added to the hot melt is small.

That is, the present invention provides (a) asphalt-based hot melt 10
0 parts by weight, (b) 5 to 50 parts by weight of ammonium halide powder with an average particle diameter of 60 μm or less, and (C) 0 to 10 parts by weight of an antimony-based flame retardant aid and/or a boron-based flame retardant aid. The present invention provides a flame-retardant asphalt-based hot melt composition.

The present invention will be explained in detail below.

The asphalt-based hot melt of the present invention having asphalt as one of its components is a composition manufactured by heating, melting and kneading the following compounds (a) to (d), and the composition ratio of each component is determined according to each application. It is determined by taking into consideration the required physical properties.

(a) Straight asphalt and/or plain asphalt (b) Tackifying resins, such as rosins such as rosin and modified rosin, terpene resins such as polymers such as β-pinene and dipentene, and monomers having 5 to 9 carbon atoms. Aliphatic or aromatic low molecular weight hydrocarbon resins obtained by polymerization, so-called petroleum resins, etc. (C) Base polymers, such as low density polyethylene,
Thermoplastic resins such as ethylene/vinyl acetate copolymer, styrene/butadiene block copolymer, styrene/imprene/styrene block copolymer, ethylene/ethyl acrylate copolymer, ethylene/vinyl acetate/maleic anhydride terpolymer, atactic polypropylene, etc. (d) Other additives, such as Z6-Tart
-Butyl-ρ-cresol, L12-methylenebis(
Ammonium halides in the present invention include antioxidants such as 2,6-sheet tθrt-butyl-phenol), plasticizers such as dioctyl phthalate and dibutyl phthalate, fillers such as calcium carbonate and clay, etc. Powders include ammonium chloride, ammonium bromide, and ammonium iodide powders, with ammonium chloride and ammonium bromide powders being preferred. Each powder is an aggregate of particles with an average particle diameter of 30 μm or less. If the average particle diameter exceeds 50 μm, it is not preferable because it adversely affects the workability, adhesive properties, and other physical properties of the flame-retardant asphalt-based hot melt composition.

In addition, if the ammonium halide powder is surface-treated with an organic substance, the dispersibility of the powder will be improved, so the physical properties such as flame retardancy, workability, and adhesiveness of the composition of the present invention will be improved, which is preferable. . As the organic substance for the surface treatment, all those generally known as surface treatment agents for inorganic powders filled in organic polymers can be used. Examples include (1) coupling agents such as silane and titanium, (2) surfactants, and (2) higher saturated and/or unsaturated fatty acids or salts thereof, but from an economical point of view, surfactants are advantageously used.

Specifically, the surfactants used in the present invention include anionic surfactants such as sodium dodecylbenzenesulfonate and dioctyl sodium sulfosuccinate; cationic surfactants such as distearyldimethylammonium chloride and laurylamine acetate; Aliphatic amine acetate surfactant of aliphatic amine acetate;
Nonionic surfactants such as sorbitan monolaurate and polyoxyethylene/polyoxypropylene ethyl alcohol ether. Among these surfactants, aliphatic amine acetate-based surfactants are particularly preferred.

In the present invention, as a method for surface-treating the surface of ammonium halide particles with the organic substance, any known method for each organic substance can be applied. For example, in the case of surface treatment with sodium dodecylbenzenesulfonate, there is a treatment method in which a certain amount of the surfactant aqueous solution is sprayed onto the top of ammonium halide powder while stirring, and then the powder is dried.

The amount of at least one type of ammonium halide necessary to obtain the effects of the present invention is 5 to 50 parts by weight, preferably 10 to 40 parts by weight, per 100 parts by weight of the asphalt hot melt.

If it exceeds 50 parts by weight, the workability and flow characteristics of the flame-retardant asphalt-based hot melt composition will deteriorate, and at the same time, various physical properties after solidification will also deteriorate, which is not preferable.

In addition, if it is less than 5 parts by weight, the flame retardant effect will be small.
Undesirable.

Examples of the antimony-based flame retardant aids of the present invention include antimony trioxide, potassium antimonate, and antimony tetroxide, and representative examples of the boron-based flame retardant aids include zinc borate. The amount of the flame retardant aid required to obtain the effects of the present invention is 0 parts by weight per 100 parts by weight of asphalt hot melt.
10 to 10 parts by weight. Within this addition amount range, the flame retardancy of the composition of the present invention increases as the addition amount increases.

However, even if more than 10 parts by weight is added, no improvement in the effect of the addition can be expected, and on the contrary, the physical properties of the flame-retardant hot melt composition will deteriorate, which is not preferable.

As a method for mixing the components of the flame-retardant asphalt-based hot melt composition of the present invention, a known method used for producing hot melt can be used as is.

For example, there is a method in which asphalt-based hot melt is melted in a hot melt stirring pot, and then at least one type of ammonium halide powder and a flame retardant additive are gradually added while stirring to thoroughly melt and mix.

The present invention will be explained in more detail by way of examples below.

Example 1 An asphalt-based hot melt having the following composition ratio was produced in a hot melt stirring pot at 160 to 170°C.

Straight asphalt senso (button 8 pass hit concubine t
Coification 100M Petroleum Resin Petroshiosu 80 Mikata Sekika 10 1. When producing the hot melt, first,
Melt straight asphalt at 160-170℃,
Then, a petroleum resin was gradually added and kneaded with stirring, and after thorough melt-mixing, a pellet of ethylene-vinyl acetate copolymer was added and kneaded in the same manner. After confirming uniform mixing, production was completed.

100 grams of the asphalt-based hot melt was placed in the hot melt stirring pot and melted at 160 to 170° C., and then 60 ammonium chloride particles having an average particle size of 18 μm were gradually added and kneaded while stirring. After the addition was complete, the mixture was stirred for an additional 10 minutes. The resulting flame-retardant asphalt-based hot melt melt was heated to 1509/rr? using a 1 mil doctor blade.
It was applied to a uniform thickness on a glass roving cloth. The workability (flow characteristics) of the melt was as good as that without the addition of ammonium chloride.

A test piece was cut out from the cooled coated glass cloth and JI
A flame retardancy test according to SK 7201 was conducted. Table 1
As shown in Figure 2, the oxygen index was extremely high at 35.5, and the flame retardance was extremely high.

Example 2 The same procedure was carried out except that ammonium chloride with an average particle diameter of 20 μm was used instead of 50 gr of ammonium chloride in Example 1, which was surface-treated with an aliphatic amine acetate surfactant (manufactured by Kao Soap, trade name: Acetamine). A coated glass cloth was obtained using the same recipe and 9 procedures as in Example 1. The workability (flow characteristics) of the flame-retardant asphalt-based hot melt was similar to that of Example 1 and was preferable.

Further, as shown in Table 1, the oxygen index was 5a7, and the flame retardance was further increased compared to Example 1.

Example 5 In place of 50 gr of ammonium chloride in Example 1, 10 gr of ammonium chloride treated on the surface of Acetami 7 in Example 2.
and antimony trioxide (manufactured by Nippon Seiko ■, product name: ATOx)
-8) A coated glass cloth was obtained using the same recipe and procedure as in Example 1 except that 2.5 g 1' was used. The workability (flow characteristics) of the melt of the composition was the same as that of Example 1, and the flame retardancy of the composition was also high, with an oxygen index of 32.5. The results are shown in Table 1.

Example 4 A coated glass cloth was obtained using the same recipe and two steps as in Example 2, except that 7.5 g of antimony trioxide from Example 6 was further added to the composition of Example 2. The workability of the composition is good without any problems, and the flame retardance is also oxygen index 4 &
It was extremely high at 5. The results are shown in Table 1.

Example 5 The same procedure was carried out except that instead of 50 gr of surface-treated ammonium chloride in Example 40, 15 particles of surface-treated ammonium chloride in Example 40 and 15 gr of ammonium bromide having an average particle diameter of 20 μm and surface-treated with acetamine in Example 2 were used. A coated glass cloth was obtained using the same recipe and 9 procedures as in Example 4. The workability of the melt of the composition and the flame retardance of the composition were excellent as shown in Table 1.

Comparative Example 1 Acetamine surface treatment of Example 4 ammonium chloride 50g
, , and antimony trioxide Z5gr, Example 2
55 gr of acetamine surface treated ammonium chloride of Example 3 and 12.5 gr of antimony trioxide of Example 3.

A coated glass cloth was obtained using the same recipe and procedure as in Example 4 except that . Although the flame retardance of the composition was high, the fluidity of the melt of the composition was poor (7J') and the workability was reduced. The results are shown in Table 1.

The same formulation as in Example 5 except that Laugh-in (manufactured by Toyo Soda Co., Ltd., trade name) Toyoparax A-70) tl- was used;
A flame-retardant asphalt-based composition was obtained through nine operational steps. During the manufacture of the composition, toxicity 1 due to decomposition of chlorinated paraffins
Hydrogen chloride gas, which is corrosive to equipment, was generated. Furthermore, the molten composition foamed due to gas generation, resulting in poor workability during application onto glass cloth. Furthermore, there was a drawback that bubble marks remained on the coated surface. The results are shown in Table 1.

Comparative Example 3 Comparative Example 10 Surface treatment Comparative Example 2 instead of ammonium chloride
A coated glass cloth was obtained using the same recipe and procedure as in Comparative Example 1 except that 50 gr of chlorinated paraffin was used.

The defects described in Comparative Example 2 were even more severe.

The results are shown in Table 1.

Comparative Example 4 Example 20 Surface Treatment A coated glass cloth was obtained using the same recipe and procedure as in Example 2 except that aluminum hydroxide (manufactured by Nippon Light Metal Co., Ltd., B105) was used instead of ammonium chloride. Although the workability of the composition was good and there were no problems, the flame retardancy was low at an oxygen index of 30.0. The results are shown in Table 1.

Comparative Example 5 A coated glass cloth was obtained using the same recipe and procedure as in Comparative Example 1, except that 50 gr of aluminum hydroxide from Comparative Example 4 was used instead of ammonium chloride from Comparative Example 1. As shown in Table 1, the workability of the composition 1 was not favorable, and the flame retardancy was also low.

The results are shown in Table 1.

Claims (3)

[Claims] (1) (a) 100 parts by weight of an asphalt-based hot melt containing asphalt as one of its components, (b) 5 to 50 parts by weight of at least one type of ammonium halide powder having an average particle size of 30 μm or less, (C) Antimony-based powder A flame-retardant asphalt-based hot melt composition comprising θ to 10 parts by weight of a combustion aid and/or a boron thread flame retardant aid. (2) The flame-retardant asphalt-based hot melt composition according to claim (1), wherein the ammonium halide powder is surface-treated with an organic substance. (3) Claim No. 1 in which the organic substance is a surfactant (
The flame-retardant asphalt-based hot melt composition according to item 1) or item (2).