JPS6153348B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel triazine-based adduct compound and a flame-retardant polyamide composition containing the triazine-based adduct compound. More specifically, the present invention relates to a novel triazine-based addition compound that is particularly useful as a flame retardant for polyamide, and a triazine-based addition compound that has a high degree of flame retardancy and makes it possible to obtain molded products with good appearance and physical properties. The present invention relates to a flammable polyamide composition. It is already known that melamine, cyanuric acid, isocyanuric acid, etc. are blended as flame retardants in order to impart flame retardancy to polyamide (for example, Japanese Patent Publication No. 47-41745, Japanese Unexamined Patent Publication No. 1983-1983). 39750
Publications, etc.). However, in polyamide compositions containing these known flame retardants, the flame retardant sublimes during molding and contaminates the mold, or when the resulting molded product absorbs moisture or during use, the flame retardant is removed. has the disadvantage that it precipitates (bleeds out) on the surface of the molded product in the form of fine powder, impairing the aesthetic appearance of the molded product. In addition, cyanuric acid and isocyanuric acid are said to have a greater flame retardant effect on polyamide than melamine, but when cyanuric acid, isocyanuric acid, etc. are used as flame retardants, the above disadvantages In addition, cyanuric acid and isocyanuric acid have a tendency to decompose during molding, so there is a drawback that foaming tends to occur locally in molded products. In order to improve the drawbacks of known flame retardants such as melamine, cyanuric acid, and isocyanuric acid, an equimolar reaction product with melamine and cyanuric acid, that is, melamine cyanurate, is used as a flame retardant. It has also been proposed to
53-31759). However, when melamine cyanurate is used, the drawbacks of melamine, cyanuric acid, isocyanuric acid, etc. mentioned above can be improved to a considerable extent, but this melamine cyanurate does not have the flame retardant properties that were intended for its original purpose. The imparting effect tends to be rather low compared to melamine and cyanuric acid, and therefore it is still not sufficient to impart high flame retardancy to polyamides, which is required in applications such as electrical component materials. No, no. Furthermore, in order to improve the drawbacks of melamine, cyanuric acid, isocyanuric acid, etc., it has already been proposed to use melamine derivatives such as methylene dimelamine and ethylene dimelamine as flame retardants for polyamide (Unexamined Japanese Patent Publication No. Publication No. 53-47451, Japanese Patent Application Laid-Open No. 56-22347, etc.). However, according to the research conducted by the present inventors, although the effect of imparting flame retardancy of these melamine derivatives is superior to that of the aforementioned melamine cyanurate, it cannot be said that it is still fully satisfactory. There is still room for improvement in terms of gender. As a result of extensive research aimed at overcoming the drawbacks of conventionally known flame retardants including melamine, the present inventors found that cyanuric acids were added to specific triazine compounds such as ethylene dimelamine in a ratio of 1:1. Alternatively, a new triazine-based adduct compound added at a molar ratio of 1:2 can impart extremely excellent flame retardancy to polyamide, and furthermore, it does not contaminate the mold or cause foaming when molding the polyamide. The present invention was achieved based on the discovery that the flame retardant does not bleed out on the surface of the molded product even when stored for a long period of time. That is, the present invention provides the formula [] (In the formula, R represents a divalent hydrocarbon residue having 1 to 12 carbon atoms) is an addition compound of a triazine compound represented by the following formula and cyanuric acid and/or isocyanuric acid in a molar ratio of 1:1 or 1:2. The present invention provides triazine-based addition compounds. Furthermore, the present invention also provides a flame-retardant polyamide composition in which the above triazine-based addition compound is blended with a polyamide. Next, the present invention will be explained in detail. The novel triazine-based addition compound of the present invention has the formula [] (In the formula, R represents a divalent hydrocarbon residue having 1 to 12 carbon atoms) and cyanuric acid and/or isocyanuric acid are added in a molar ratio of 1:1 or 1:2 (triazine Compounds: cyanuric acid and/or isocyanuric acid)
It can be manufactured by adding at a ratio of . In addition, when carrying out this addition reaction,
Cyanuric acid and/or isocyanuric acid may be added to the reaction system in excess of the above addition ratio, but even in such a case, the resulting product will be added at the above molar ratio of 1:1 or 1:2 addition. A compound or a mixture thereof. The triazine compounds represented by the above formula [] are well-known compounds, and these compounds and production methods are described in US Pat. No. 2,544,071. Specific examples of the triazine compound represented by the above formula [] include methylene dimelamine (R = methylene group), ethylene dimelamine (R = ethylene group), trimethylene dimelamine (R = trimethylene group), Tetramethylene dimelamine (R=
tetramethylene group), hexamethylene dimelamine (R=hexamethylene group), dodecamethylene dimelamine (R=dodecamethylene group), and the like. The cyanuric acid and isocyanuric acid added to the above triazine compound are expressed by the following formula [] and formula [], respectively:

【formula】

These cyanuric acids and isocyanuric acids have a keto-enol tautomer relationship, and in reality, they do not exist independently. Therefore, in the following description, these two will be represented by the expression cyanuric acid without making any particular distinction between them. The triazine-based addition compound of the present invention is also considered to be a type of salt of the triazine-based compound of the formula [], such as ethylene dimelamine, which is a weak base, and cyanuric acid, which is a weak acid. The triazine-based addition compound of the present invention can be produced by causing an addition reaction in a solvent that dissolves at least one, preferably both, of the triazine-based compound of the formula [] such as ethylene dimelamine and cyanuric acid. . Examples of solvents that dissolve both triazine compounds and cyanuric acid include dimethyl sulfoxide,
Examples include diethyl sulfoxide, N·N-dimethylformamide, N·N-dimethylacetamide, N-methyl-2-pyrrolidone, ethylene glycol, diethylene glycol, methyl cellosolve, ethyl cellosolve, dioxane, and water. These solvents can be used alone or in combination, and can also be used in combination with solvents other than those exemplified above. When carrying out the addition reaction between a triazine compound and cyanuric acid, the reaction is preferably carried out under heating in order to increase the solubility in the solvent used and improve the yield. The reaction temperature is not particularly limited, but is usually selected from the range of room temperature to 300°C. If the reaction temperature exceeds 300°C, the thermal decomposition of the raw materials becomes intense, so such an excessively high temperature is not practically preferred. The preferred reaction temperature range is 50-200°C. This reaction is usually carried out under normal pressure, but may be carried out under reduced pressure or increased pressure, if desired. There is no particular limitation on the relative ratio of the raw material compounds introduced into the reaction system when carrying out the above reaction, but since the reaction product is an addition compound with a molar ratio of 1:1 or 1:2, it is economical. Considering this, it is preferable to introduce the triazine compound of the formula [] and cyanuric acid into the reaction system in a molar ratio of 1:1 or 1:2. Among the triazine-based addition compounds of the present invention, cyanuric acid 1:1 addition compound (compound in which 1 mole of cyanuric acid is added to 1 mole of triazine-based compound)
has an IR spectrum as shown in the attached Figure 1, and a cyanuric acid 1:2 addition compound (a compound in which 2 moles of cyanuric acid is added to 1 mole of a triazine compound) has an IR spectrum as shown in the attached Figure 1. They have IR spectra as shown in the figure, and both are white solids. Also, cyanuric acid 1:1
Both the addition compound and the cyanuric acid 1:2 addition compound decompose at temperatures above 300°C and are poorly soluble in water, alcohols, ketones, dioxane, dimethyl sulfoxide, etc. The novel triazine-based addition compounds of the present invention are extremely useful as flame retardants for thermoplastic resins such as polyamides. When this addition compound is used as a flame retardant for thermoplastic resin, it can impart good flame retardancy with a small amount of addition, and it does not generate toxic gas when burned. Furthermore, it has an excellent property of not bleeding out from the resin molded product. In particular, it is practically advantageous that R in the triazine compound moiety (formula []) of the triazine adduct compound of the present invention is a divalent hydrocarbon residue having 1 to 6 carbon atoms, and furthermore, R is an ethylene group. are particularly advantageous. The novel triazine-based addition compound of the present invention exhibits the above-mentioned superior properties, especially when used as a flame retardant for polyamide, compared to conventionally proposed flame retardants for polyamide. Particularly advantageous. That is, the polyamide composition in which the novel triazine-based addition compound of the present invention is blended as a flame retardant has the unprecedented advantage of (1) exhibiting a high degree of flame retardancy with a small amount of flame retardant blended; as well as (2)
Since only a small amount of flame retardant is required, there is no need to worry about adverse effects on the excellent physical properties of polyamide, (3) contamination of the mold during molding, and (4)
It has many excellent features such as the molded product does not foam and (5) the flame retardant does not bleed out onto the molded product surface. Specific examples of polyamides include polylactams such as nylon 6, nylon 11, and nylon 12, polyamides obtained from dicarboxylic acids and diamines such as nylon 66, nylon 610, and nylon 612, nylon 6/66, and nylon 6/66. Copolymerized polyamides such as /610, and mixtures thereof can be mentioned. When the novel triazine-based addition compound of the present invention is blended into polyamide as a flame retardant, the blending amount is 1 to 65 parts by weight per 100 parts by weight of polyamide.
In particular, it is preferably 1 to 40 parts by weight. The flame-retardant polyamide composition described above may contain known additives such as antioxidants, lubricants, and inorganic fillers. As mentioned above, the triazine-based addition compound of the present invention is extremely useful as a flame retardant for thermoplastic resins such as polyamide, but its use is not limited to this, and it can be used as a flame retardant for other types of resins. It can be used alone or in combination with other known compounds for various purposes such as flame retardants, fiber treatment agents, insecticides, fungicides, and herbicides. Next, Examples and Comparative Examples of the present invention will be shown. Example 1 600 ml of dimethyl sulfoxide was added to 13.9 g (0.05 mol) of ethylene dimelamine, and the mixture was heated to 100°C to obtain an ethylene dimelamine solution. Separately, 100 ml of dimethyl sulfoxide was added to 6.45 g (0.05 mol) of cyanuric acid, and the mixture was heated to 100°C to obtain a cyanuric acid solution. When a 100°C cyanuric acid solution was added to the ethylene dimelamine solution while keeping it at 100°C, a white precipitate was instantly formed. The reaction mixture was stirred for an additional 30 minutes while maintaining the temperature at 100°C, and the precipitate was filtered while hot. The filtered precipitate was thoroughly washed with hot dimethyl sulfoxide, and then thoroughly washed with a large amount of hot water and acetone. By drying this precipitate, 18.5 g of white powder was obtained. The elemental analysis values and physical properties of the obtained white powder are shown below. Analysis value:
C 32.37%; H 4.20%; N 51.55% Calculated value (C ₈ N ₁₂ H ₁₄・C ₃ N ₃ H ₃ O ₃ ):
C 32.43%; H 4.18%; N 51.60% Melting point: Decomposition (decomposition start temperature 330°C; TGA method) Solubility (room temperature): Water, alcohols, ketones,
IR spectrum that is poorly soluble in dioxane and dimethyl sulfoxide: Figure 1 (KBr method) For reference, the IR spectrum of a mixture of ethylene dimelamine and cyanuric acid in a molar ratio of 1:1 (KBr
Figure 2) is attached. The IR spectrum in Figure 1 is that of Figure 2 (mixture).
It is clearly different from the IR spectrum, especially from 2750
Absorption peculiar to ammonium salts is observed at 2800 cm ^-1 and 1600 cm ^-1 . From the above results, the obtained white powder was identified as an addition compound of ethylene dimelamine and cyanuric acid at a molar ratio of 1:1. Example 2 In Example 1, the amount of cyanuric acid used was 12.9g.
Similar reactions and treatments were carried out except that (0.1 mol) was used instead. 25.2 g of white powder was obtained. The elemental analysis values and physical properties of the obtained white powder are shown below. Analysis value:
C 31.31%; H 3.71%; N 46.95% Calculated value (C ₈ N ₁₂ H ₁₄・2C ₃ N ₃ H ₃ O ₃ ):
C 31.34%; H 3.73%; N 47.01% Melting point: Decomposition (decomposition start temperature 340°C; TGA method) Solubility (room temperature): Water, alcohols, ketones,
IR spectrum that is poorly soluble in dioxane and dimethyl sulfoxide: Figure 3 (KBr method) For reference, the IR spectrum of a mixture of ethylene dimelamine and cyanuric acid in a molar ratio of 1:2 (KBr
Figure 4) is attached. The IR spectrum in Figure 3 is that of Figure 4 (mixture).
It is clearly different from the IR spectrum, especially from 2750
Absorption peculiar to ammonium salts was observed at 2800 cm ^-1 and 1600 cm ^-1 . From the above results, the obtained white powder was identified as an addition compound of ethylene dimelamine and cyanuric acid at a molar ratio of 1:2. Example 3 In Example 1, the amount of cyanuric acid used was 25.8g.
The same reaction and treatment were carried out except that (0.2 mol) was used instead. 25.4 g of white powder was obtained. The elemental analysis values and physical properties of the obtained white powder are shown below. Analysis value:
C 31.30%; H 3.75%; N 47.03% Calculated value (C ₈ N ₁₂ H ₁₄・2C ₃ N ₃ H ₃ O ₃ ):
C 31.34%; H 3.73%; N 47.01% Melting point: Decomposition (decomposition start temperature 340°C; TGA method) Solubility (room temperature): Water, alcohols, ketones,
Poorly soluble in dioxane and dimethyl sulfoxide IR spectrum: Same as Figure 3 From the above results, the obtained white powder was identified as an addition compound of ethylene dimelamine and cyanuric acid in a molar ratio of 1:2. Example 4 The same reactions and treatments as in Example 2 were carried out except that 16.7 g (0.05 mol) of hexamethylene dimelamine was used in place of ethylene dimelamine. 26.7 g of white powder was obtained. The elemental analysis values and physical properties of the obtained white powder are shown below. Analysis value:
C 36.40%; H 4.75%: N 42.51% Calculated value (C ₈ N ₁₂ H ₂₂・2C ₃ N ₃ H ₃ O ₃ ):
C 36.49%; H 4.73%; N 42.57% Melting point: Decomposition (decomposition start temperature 320°C; TGA method) Solubility (room temperature): Water, alcohols, ketones,
Insoluble in dioxane and dimethyl sulfoxide IR spectrum: Similar to Figure 3, 2750-2800 cm
^-1 , absorption peculiar to ammonium salts was observed at 1600 cm ^-1 . From the above results, the obtained white powder has a molar ratio of hexamethylene dimelamine and cyanuric acid of 1:2.
It was identified as an adduct compound. Example 5 The same reactions and treatments as in Example 2 were carried out except that 20.9 g (0.05 mol) of dodecamethylene dimelamine was used in place of ethylene dimelamine. 31.1 g of white powder was obtained. The elemental analysis values and physical properties of the obtained white powder are shown below. Analysis value:
C 42.56%; H 5.89%; N 37.30% Calculated value (C ₁₈ N ₁₂ H ₃₄・2C ₃ N ₃ H ₃ O ₃ ):
C 42.60%; H 5.92%; N 37.28% Melting point: Decomposition (decomposition start temperature 315°C; TGA method) Solubility (room temperature): Water, alcohols, ketones,
Insoluble in dioxane and dimethyl sulfoxide IR spectrum: Similar to Figure 3, 2750-2800 cm
^-1 , absorption peculiar to ammonium salts was observed at 1600 cm ^-1 . From the above results, the obtained white powder has a molar ratio of dodecamethylene dimelamine and cyanuric acid of 1:2.
It was identified as an adduct compound. Example 6-7 Nylon 6 pellets 94 with a number average molecular weight of 13000
6 parts by weight of a 1:1 addition compound or a 1:2 addition compound of ethylene dimelamine and cyanuric acid in a molar ratio were blended with each part by weight, and pellets were obtained using an extruder. Injection molding from this pellet (molding temperature
(230°C) to prepare test pieces for each combustion test. Separately, add 94 parts by weight of the above nylon 6 pellets to ethylene dimelamine and cyanuric acid in a molar ratio of 1:1.
6 parts by weight of the addition compound or 1:2 addition compound and 0.5 part by weight of carbon black were blended and pellets were obtained using an extruder. A test piece for a bleed-out test was prepared from this pellet by injection molding (molding temperature: 230°C). Comparative Example 1-2 In the production process of each test piece in Examples 6-7 above, the same amount of ethylene dimelamine and cyanuric acid was used instead of the 1:1 addition compound or the 1:2 addition compound in the molar ratio. A test piece for a combustion test and a test piece for a bleed-out test were prepared in the same manner except that melamine or cyanuric acid was used. [Flame retardancy test and bleed-out test] The flame retardancy of the test piece and the bleed-out of the flame retardant onto the surface of the test piece were evaluated as follows. (1) Flame retardance A test piece measuring 5 inches long, 1/2 inch wide, and 1/32 inch thick was subject 94 (UL) specified by Underwriters Laboratories, Inc.
-94), a combustion test was conducted. (2) Bleed-out A bleed-out test piece of 80 mm in length and width and 2 mm in thickness was placed in air at a relative humidity of 95% and a temperature of 40°C for 10 minutes.
The test piece was left to stand for several days, and bleed-out of the flame retardant onto the surface of the test piece was observed with the naked eye. The test results are shown in Table 1.

[Table] Lost.

[Brief explanation of the drawing]

Figure 1 shows the IR spectrum of an addition compound of ethylene dimelamine and cyanuric acid in a molar ratio of 1:1 (KRr method); Figure 2 shows the IR spectrum of a mixture of ethylene dimelamine and cyanuric acid in a molar ratio of 1:1. (Same); Figure 3 shows the IR spectrum (KBr method) of an addition compound of ethylene dimelamine and cyanuric acid at a molar ratio of 1:2; and Figure 4 shows the molar ratio of ethylene dimelamine and cyanuric acid at 1:2. :2 mixture
IR spectra (same);

Claims (1)

[Claims] 1 Formula [] (In the formula, R represents a divalent hydrocarbon residue having 1 to 12 carbon atoms) is an addition compound of a triazine compound represented by the following formula and cyanuric acid and/or isocyanuric acid in a molar ratio of 1:1 or 1:2. Triazine-based addition compounds. 2. The triazine-based addition compound according to claim 1, wherein R in the formula [] is a divalent hydrocarbon residue having 1 to 6 carbon atoms. 3. The triazine-based addition compound according to claim 1, wherein R in formula [] is an ethylene group. 4 Polyamide has the formula [] (In the formula, R represents a divalent hydrocarbon residue having 1 to 12 carbon atoms) is an addition compound of a triazine compound represented by the following formula and cyanuric acid and/or isocyanuric acid in a molar ratio of 1:1 or 1:2. A flame-retardant polyamide composition containing a triazine-based addition compound. 5. The flame-retardant polyamide composition according to claim 4, wherein R in the formula [] of the triazine-based addition compound is a divalent hydrocarbon residue having 1 to 6 carbon atoms. 6. The flame-retardant polyamide composition according to claim 4, wherein R in formula [] of the triazine-based addition compound is an ethylene group.