JPH08231517A - Production of triazine sulfate composition - Google Patents

Abstract

PURPOSE: To obtain the subject compound preventing the elution of components high in water solubility, useful as a flame retardant and having low toxicity and good acid resistance by reacting an aminotriazine compound with sulfuric acid in a specific molar ratio. CONSTITUTION: An aminotriazine compound such as a compound of the formula (R) is amino, a 1-4C alkyl, a 6-10C aryl) is reacted with sulfuric acid in a molar ratio of 1:(0.1-1), preferably 1:(0.2-0.8), to obtain the objective compound. On the consideration of the water resistance, the reaction product is preferably washed with water until when the pH of the washing liquid used for the washing reaches >=5.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an aminotriazine sulfate composition.

[0002]

2. Description of the Related Art Various flame retardants have been used to make flame-retardant thermoplastic resins flame-retardant. Among various flame retardants, halogen-based flame retardants include hydrogen bromide, which is generated during combustion.
Recently, not only acidic gases such as hydrogen chloride, but also the generation of dioxins has been regarded as a problem. Further, the phosphorus-based flame retardant has the problems of explosiveness and phosphine generated during molding. Therefore, non-halogen-non-phosphorus flame retardants have been receiving attention.

Metal hydroxides such as magnesium hydroxide are non-halogen-non-phosphorus flame retardants and have a problem that they have low toxicity but poor acid resistance. Further, in order to make it flame-retardant, a large amount must be blended, which causes a problem of impairing the properties of the resin.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have found that aminotriazine sulfate is effective as a flame retardant having improved acid resistance and have already proposed it (Japanese Patent Application No. 6-1).
84828). As a result of further research on a method for preparing aminotriazine sulfate, when aminotriazine sulfate was produced by excessively reacting an aminotriazine compound with sulfuric acid, a resin containing this showed flame retardance. However, it was found that there is a problem that components having high solubility in water are eluted. Then, the objective of this invention is to develop the method of manufacturing the aminotriazine sulfate which suppressed the elution with respect to water.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above-mentioned problems, and as a result, by reacting an aminotriazine compound and sulfuric acid at a molar ratio of 1: 0.1 to 1, excellent water resistance is obtained. The inventors have found that a triazine sulfate composition can be obtained and completed the present invention.

That is, the present invention is a method for producing an aminotriazine sulfate composition, which comprises reacting an aminotriazine compound and sulfuric acid in a molar ratio of 1: 0.1-1.

The aminotriazine compound used in the present invention is a compound obtained by substituting at least one amino group into triazine or a substituted triazine substituted with a hydrocarbon group or the like. The most common triazine is 1,3,5-triazine. Examples of the hydrocarbon group substituted with triazine include a methyl group, an ethyl group, a propyl group and the like having 1 to 1 carbon atoms
An aryl group having 6 to 10 carbon atoms such as an alkyl group having 4 or a phenyl group is preferable. Up to 3 amino groups can be substituted, and any of these compounds can be used in the present invention. The aminotriazine compound that can be preferably used in the present invention can be represented by the following general formula.

[0008]

Embedded image

(However, R ₁ is an amino group, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms.) Specific examples of the aminotriazine compound which can be preferably used in the present invention are shown below. , Melamine, benzoguanamine, methylguanamine, etc., which can be used alone or in combination.

The particle size of these aminotriazine compounds is not particularly limited, but those having an average particle size of 0.1 to 50 μm can be preferably used.

The sulfuric acid can be used without particular limitation as long as it is generally available. The concentration of sulfuric acid is not particularly limited, and either concentrated sulfuric acid or diluted sulfuric acid can be used, but it is preferable to use diluted sulfuric acid from the viewpoint of handling.

The reaction ratio between the aminotriazine compound and sulfuric acid is a molar ratio of 1: 0.1-1 and preferably 1: 0.2-0.
8 When the molar ratio of sulfuric acid is less than 0.1, the effect of imparting water resistance to the aminotriazine compound is low, which is not preferable. When the molar ratio of sulfuric acid is greater than 1,
It is not preferable because a large amount of aminotriazine sulfate, which has a high solubility in water that has reacted excessively with sulfuric acid, is produced, and the effect of improving the water resistance is reduced.

The reaction method of the aminotriazine compound and sulfuric acid is not particularly limited, and a conventionally known method can be used. For example, a method in which an aminotriazine compound is previously dispersed in water and sulfuric acid is added little by little or at once at room temperature, a method in which sulfuric acid is added while stirring while crushing the aminotriazine compound in a ball mill at room temperature, sulfuric acid Examples thereof include a method of adding an aminotriazine compound.

The reaction conditions are not particularly limited,
The temperature may be normal temperature, and the pressure may be any of reduced pressure, normal pressure and increased pressure.

The reaction product thus obtained can be added to the resin as it is as a flame retardant. However, unreacted sulfuric acid or aminotriazine sulfate having low water resistance remains, so that it is mixed with the resin to form a composition. There is a risk of causing mold stains and the like during the molding process. In order to prevent such mold stains, it is preferable to thoroughly wash the reaction product obtained by the above-mentioned method with water. Considering the water resistance of aminotriazine sulfate, it is preferable that the washing liquid used for washing be washed with water until pH = 5 or more.

The aminotriazine sulfate composition produced in the present invention is considered to be a mixture of various salts having different reaction ratios, and may contain the raw material aminotriazine compound in an unreacted state.

The aminotriazine sulfate composition of the present invention is useful as a flame retardant for thermoplastic resins. Examples of the thermoplastic resin used include polyolefins such as polyethylene and polypropylene, polystyrene, AS resin, A
Styrene resin such as BS resin, vinyl resin such as polymethylmethacrylate, polyvinyl acetate, polyvinyl alcohol, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate resin, polyether resin, and SBR, NBR, polybutadiene, poly Examples thereof include elastic polymers such as isoprene, and various resins modified with these, and polyolefin is particularly preferably used. These thermoplastic resins can be used alone or in combination.

The amount of the aminotriazine sulfate composition compounded is 10 to 300 parts by weight, preferably 15 to 250 parts by weight, based on 100 parts by weight of the thermoplastic resin. When the blending amount is less than the lower limit value, a sufficient flame retardant effect cannot be obtained,
If it is more than the upper limit, moldability and impact resistance decrease,
Not only is the specific gravity increased, but stable kneading work becomes difficult, which is not preferable.

As other components, if necessary, conventionally known antioxidants (phenolic compounds, phosphorus compounds, sulfur compounds, etc.), weather resistance, etc., as long as the effects of the aminotriazine sulfate composition are not impaired. Agents (benzophenone, salicylate, benzotriazole, hindered amine, etc.), metal deactivators, colorants, antistatic agents (anionic, cationic, nonionic, amphoteric),
Lubricants (fatty acids, fatty acid amides, fatty acid metal salts, fatty acid esters, hydrocarbons, etc.), nucleating agents (metal salt systems, sorbitol, etc.), fillers (talc, calcium carbonate, barium sulfate, glass fibers, mica, etc.), It may contain an anti-blooming agent or a flame retardant aid (such as thermally expansive graphite).

The mixing order and mixing method of each of these components are not particularly limited, and generally, a tumbler type blender, a V-type blender, a Henschel mixer, a ribbon mixer and the like are used by a conventional method.

[0021]

[Effect] The aminotriazine sulfate composition obtained by the present invention is useful as a non-halogen-non-phosphorus flame retardant having excellent water resistance. Although the reason why the aminotriazine sulfate composition obtained by the present invention is excellent in water resistance is not clear, sulfuric acid reacts with the surface of the aminotriazine compound, and the aminotriazine sulfate composition excellent in water resistance is aminotriazine. It is presumed that the compound surface is covered.

[0022]

EXAMPLES In order to more specifically describe the present invention, examples and comparative examples will be described below, but the present invention is not limited to these examples.

Examples and Comparative Examples Preparation and testing methods of aminotriazine sulfate composition and flame retardant resin composition are carried out as follows. The results are shown in Table 1.

(1) Synthesis of Aminotriazine Sulfate Composition 5 mol of the aminotriazine compound having the average particle size shown in Table 1 was dispersed in 1 L of water at room temperature, and sulfuric acid (concentration of the concentration in Table 1 was mixed with stirring). 40% by weight) was gradually added. After reacting for 1 hour, the mixture was filtered to obtain an aminotriazine sulfate composition.
For those that have been washed with water, the filtrate is p
Water was poured until H = 5 or less, and then dried.

(2) Premixing 40 parts by weight of the aminotriazine sulfate composition and 2,6-di-t-butyl-based on 100 parts by weight of polypropylene.
4-Methylphenol (Stabilizer BHT, manufactured by Sumitomo Chemical Co., Ltd.): 0.1 part by weight, dilauryl thiodipropionate (Sumilizer TPL-, manufactured by Sumitomo Chemical Co., Ltd.)
R): 0.2 parts by weight and calcium stearate (manufactured by Dainippon Ink and Chemicals, Inc.): 0.1 parts by weight were mixed and premixed with a Henschel mixer.

(3) Pelletization The above mixture was pelletized by using a vented 50 mmφ extruder.

(4) Preparation of test piece A test piece (length: 5 inches, width: 1/2 inch, thickness: 1/8 inch) was prepared from the above pellets using a 2oz injection molding machine.

(5) Mold Contamination Test The mold contamination after 1000 shots molding was evaluated with a 2oz injection molding machine.

(6) Water resistance test Using the test piece prepared by the method of (4), a temperature of 80
The change in weight after 1 hour at ° C was evaluated.

(7) Combustion test Using the test piece prepared by the method of (4), the combustibility was judged by a vertical combustion test in accordance with UL94 standard.

[0031]

[Table 1]

Claims (1)

[Claims] 1. A method for producing an aminotriazine sulfate composition, which comprises reacting an aminotriazine compound and sulfuric acid in a molar ratio of 1: 0.1-1.