JPS60243139A - Ammonium halide flame-retardant coated with unsaturated polyester resin - Google Patents

Abstract

PURPOSE:To provide a flame retardant exhibiting excellent dispersibility when compounded and kneaded with a resin, resistant to thermal discoloration, and having sufficient flame-retarding effect, by coating ammonium halide with an unsaturated polyester resin. CONSTITUTION:Particles of ammonium chloride or ammonium bromide having particle diameter of <=100mum, preferably 10-30mum are mixed with 10-50wt%, preferably 20-35wt% unsaturated polyester resin having low viscosity (preferably a resin of general-purpose grade or coating grade) and an arbitrary component selected from antimony trioxide and a diluting solvent (e.g. benzene, toluene, etc.), and are uniformly dispersed by a high-speed mixer. The obtained mixture is cured as it is and pulverized, or the mixture is pulverized by a spray drier and cured to obtain the objective flame retardant consisting of ammonium halide coated with an unsaturated polyester.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to flame retardants. More specifically, the present invention provides an ammonium halide flame retardant in which ammonium chloride or ammonium bromide (hereinafter referred to as ammonium halide) is coated with an unsaturated polyester resin.

The use of ammonium halides as flame retardants in flammable polymers is well known. However, this compound has strong self-aggregation properties, and it is known that not only does it cause clumping during storage, but when it is mixed with polymers such as polyvinyl chloride, polyethylene, and polypropylene, it also causes agglomeration due to shear during cross-contact. It is being This drawback is one of the reasons that limits the use of ammonium halides in flammable polymers.

Coating the surface of ammonium halides with surfactants, chlorinated paraffins, etc. is a method of improving the self-aggregation properties of ammonium halides, but these treatment agents can significantly reduce the heat resistance (thermal discoloration) of polyolefins, etc. This can cause the appearance of the molded product to deteriorate significantly due to deterioration or bleeding.

In addition, regarding the method of coating flame retardant with resin, urea-
A method of improving weather resistance by coating with formaldehyde resin is known (Japanese Unexamined Patent Publication No. 100544/1983).

However, since this method uses a water-soluble resin, there are various problems in applying it to ammonium halide, which is a readily water-soluble compound. Furthermore, amino resins also have the disadvantage of being susceptible to thermal discoloration.

Therefore, the inventor of the present invention conducted intensive research to solve these drawbacks, and investigated coating ammonium halide with a polymer compound that has good heat resistance and does not cause bleeding. As a result, unsaturated polyester resin was found to be suitable for this purpose. The present invention was completed based on the discovery that

The present invention will be explained in detail below.

The flame retardant of the present invention is an ammonium halide flame retardant in which ammonium halide is coated with an unsaturated polyester resin and does not cause re-agglomeration or thermal discoloration when kneaded with polyolefin or the like.

The unsaturated polyester resin is not particularly limited as long as it has a low viscosity, but general use or paint grade is preferred. The amount of unsaturated polyester resin to be used is 10 to 50% by weight, preferably 20 to 35% by weight, based on the ammonium halide, taking into consideration the coating effect and flame retardancy.

Ammonium halokenide is ammonium chloride or ammonium bromide, and those with a particle size of 100 μm or less, preferably 10 to 50 μm, are suitable; if the particle size is too large, the physical properties of the molded product after resin compounding will deteriorate. Therefore, it is undesirable. Therefore, ammonium halide needs to be pulverized as necessary.

Ammonium halide usually improves its flame retardant effect when used in combination with antimony trioxide. In carrying out the invention,
There is no problem in using antimony trioxide together.

Mixer, stirrer to mix ammonium halide or a mixture of ammonium halide and antimony trioxide with unsaturated polyester resin.

Alternatively, a mixer such as a ball mill is suitable, and if necessary, a diluting solvent is added to reduce the viscosity.

The diluting solvent is preferably a solvent that dissolves the unsaturated polyester resin and evaporates at a relatively low temperature, such as a paint solvent such as benzene, toluene, or ethyl acetate.

If an unsaturated polyester resin mixture containing ammonium halide, etc. is cured as it is and then crushed, or it is powdered using a spray dryer and then cured, the ammonium halide flame retardant coated with the unsaturated polyester resin can be cured. can get.

The flame retardant composition obtained according to the present invention does not cause agglomeration during storage, and when mixed with polyolein etc. and kneaded, it is uniformly dispersed in polyolefin etc., does not cause discoloration due to heat, and does not release. It also has excellent flammability.

EXAMPLES Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited thereto.

Production Example 1 Unsaturated Polyester Resin 69C Product Master Borac A-1
55AL, Nippon Shokubai Kagaku ■) and benzoyl peroxide paste α249 dissolved in 30 g of acetone, ammonium chloride (the reagent was ground in a ball mill with an average particle size of 10 μm).
30g of the solution (prepared to 100ml) was added and uniformly dispersed using a high-speed stirrer. The resulting mixture was spread thinly on a Teflon plate, the acetone was evaporated by air drying, and then the mixture was placed in an open oven at 150° C. and cured for 50 minutes. The obtained film-like solid was pulverized to a particle size of 30 mesh or less using an ultracentrifugal pulverizer. No self-agglomeration was observed in the obtained flame retardant.

Manufacturing Example 2 Unsaturated Polyester/L/Tree IF! j259 (trade name Borac G-155AL, Nippon Shokubai Kagaku ■), 12.5 g of benzoyl peroxide paste, and benzene 125Q were mixed with ammonium chloride 4 ground to an average particle size of 10 μm.
00g and antimony trioxide (trade name ATOX-8.
Add Nippon Concentrate■) 1009, SV Any1 Kneader
(manufactured by Haiyama Seisakusho), the benzene was removed under reduced pressure while being dispersed. The resulting paste mixture was spread thinly on a Teflon plate and placed in an oven at 150°C to cure for 30 minutes.

The obtained solid was pulverized using the centrifugal pulverizer of Example 1 to a particle size of 3° mesh or less. No self-aggregation was observed in the obtained flame retardant composition.

Production Example 5 Unsaturated Polyester Resin 69 (Product Name Epoch N-5
7OL, Nippon Shokubai Kagaku■), Benzoyl Peroxide Pace)
(Add ammonium chloride (reagent) 302 to a solution of 124 g dissolved in 100 g of acetone, and use a 500 mJ porcelain ball mill (ball φ20+as).

250-fill) at a rotation speed of 60 times/min for 20 hours.

After separating the obtained slurry from the balls, it was dried using a spray dryer under the conditions of an inlet temperature of 80°C, an outlet temperature of 40°C, and a drying air flow rate of α5 gl/min.

The obtained white powder was placed in a glass Petri dish and cured for 60 minutes in an oven at 150°C to obtain a finely powdered ammonium rhodanide flame retardant coated with an unsaturated polyester resin. Self-aggregation was not observed in the flame retardant.

Production Example 4 Ammonium bromide coated with an unsaturated polyester resin was obtained in the same manner as in Example 1 except that ammonium chloride in Example 1 was replaced with ammonium bromide. Self-agglomeration was not observed in this flame retardant either.

Manufacture Comparative Example 1 The unsaturated polyester resin 69 of Example 1 was replaced with the melamine alkyd resin 1! L39 (product name Melami A1, NOF ■)
Ammonium chloride coated with a melamine alkyd resin was obtained in the same manner as in Example 1 except that benzoyl peroxide was not added. The flame retardant did not show self-aggregation, but was colored pale yellow.

Use example 1 The flame retardant obtained in Example 1 was added to polyethylene (Petrocene 20
3. Toyo Soda Kogyo■) 100 parts by weight to 18 parts by weight are mixed and kneaded, and molded using an injection molding machine at a cylinder temperature of 170°C and a mold temperature of 50°C, 150 x 110 x 2 m.
It was molded to the size of. The resulting molded product was visually tested for dispersibility and the presence or absence of coloration. The dispersibility was good, no aggregation of the flame retardant was observed, and no coloration of the molded product was observed.

In addition, flame retardancy was evaluated based on J.K. SK 7201. These results are shown in Table 1.

Usage examples 2 to 5. Reference Examples 1 to 3 Molding and test evaluation were conducted in the same manner as in Use Example 1 using the formulations shown in Table 1. The results are shown in Table 1.

As can be seen from the examples above, the flame retardant of the present invention has good dispersibility when mixed and kneaded with resin, does not cause any coloring when mixed into molded products, and is even more effective when coated with unsaturated polyester resin. It can be said that it is a useful flame retardant that does not reduce the flame retardant effect of.

Patent applicant: Toyo Soda Kogyo Co., Ltd.

Claims (1)

[Claims] An ammonium halide flame retardant comprising ammonium chloride or ammonium bromide coated with an unsaturated polyester resin.