JPH1129662A - Flame retardant resin composition and its molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin composition, hardly deteriorating mechanical strength without producing scattered materials such as expanded graphite at the time of combustion and without having any color difficult to carry out the color matching and having a high level of flame retardance, further excellent light resistance and high fluidity by compounding a polyolefin having a melt index within a specific range with a sulfate of an aminotriazine compound. SOLUTION: This resin composition is obtained by compounding (A) 50-90 pts.wt. polyolefin-based resin having 7-100 g/10 min melt index at 230 deg.C temperature under 2.16 kg load (e.g. a polypropylene resin) with (B) 10-50 pts.wt. sulfate of an aminotriazine compound [e.g. a compound represented by formula I or II (R<1> and R<2> are each amino, a 1-5C alkyl, etc.; X is O, S or NH)] (e.g. melamine sulfate). The total amount of the components A and B is 100 pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a useful material for molding exterior materials (housings, etc.) and interior parts (connectors, board holders, etc.) requiring flame retardancy in home electric appliances, OA products, automobiles and the like. The present invention relates to a flammable resin composition and a molded article thereof.

[0002]

2. Description of the Related Art Synthetic resins such as polyolefins, polystyrenes, polyamides, polyesters, polyethers, polycarbonates, phenolic resins and epoxy resins have been used in a wide range of fields as molding materials, taking advantage of their excellent properties. However, since they are flammable, fire safety, that is, flame retardancy is often required for use as industrial materials. A common method of flame retarding thermoplastic resins is to incorporate a flame retardant. As the flame retardant, a halogen-based flame retardant represented by decabromodiphenyl oxide is widely used. However, it has been pointed out that when the compounded resin is burned or exposed to high heat, harmful and toxic gas and smoke are generated, and there is a concern about a corrosion phenomenon of a molding machine. Further, when a halogen-based flame retardant is contained, there is a problem that light resistance is reduced. In order to improve the above-mentioned disadvantages of halogen-based flame retardants, it has been proposed to use non-halogen-based flame retardants. For example, JP-A-8
JP-A-48812 discloses a flame-retardant resin composition in which a sulfate of a triazine compound is blended with a thermoplastic resin. However, this composition does not have sufficient flame retardancy to be used as an industrial material and lacks self-extinguishing properties. Further, JP-A-8-81583 discloses a flame-retardant resin composition in which a sulfate of a triazine compound and thermally expandable graphite are blended in a thermoplastic resin. However, although this composition has sufficient flame retardancy, it has a problem that the thermally expandable graphite expands and scatters during combustion because it contains thermally expandable graphite. Furthermore, since the heat-expandable graphite itself is colored, there is a problem that the composition becomes black and it is difficult to adjust the color of the product. Further, Japanese Unexamined Patent Publication No.
No. 231517 discloses a method for producing an aminotriazine compound sulfate composition useful as a flame retardant. However, a thermoplastic resin composition blended with an aminotriazine compound sulfate composition still has insufficient flame retardancy to be used as an industrial material.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, is low in harmful and low smoke, has little decrease in mechanical strength and the like, and furthermore, scattered matter such as expanded graphite during combustion. To provide a resin composition having a high degree of flame retardancy, high light resistance, high fluidity, suitable for injection molding, and a molded product thereof, which is free of color that does not have difficult toning. With the goal.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been completed based on the finding that a resin composition comprising a polyolefin having a melt index in a specific range and a sulfate salt of an aminotriazine compound meets the above-mentioned object. Things. That is, the present invention provides (A) a temperature of 230 ° C.,
Melt index at a load of 2.16 kg (hereinafter referred to as MI
(Which may be abbreviated as 7), comprising 50 to 90 parts by weight of a polyolefin resin having a content of 7 to 100 g / 10 min and 10 to 50 parts by weight of a sulfate salt of an aminotriazine compound (B). A flame-retardant resin composition characterized in that the total amount of the components is 100 parts by weight, and a molded article characterized by comprising the resin composition.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the resin composition of the present invention,
As the component (A), a polyolefin resin having a melt index (MI) of 7 to 100 g / 10 min at a temperature of 230 ° C. and a load of 2.16 kg is preferable. MI is 7g /
If it is shorter than 10 minutes, the flame retardancy V-2 cannot be obtained,
If it is greater than 0 g / 10 minutes, physical properties will be reduced. As the polyolefin resin, a polypropylene resin or a mixture of a polypropylene resin and a propylene-ethylene block copolymer is preferable. Polyethylene resin may be included, but the polyethylene resin alone may not reach the flame-retardant performance V-2.

The sulfate of the aminotriazine compound used as the component (B) is obtained by reacting the aminotriazine compound with sulfuric acid. As the aminotriazine compound, a compound represented by the general formula (I) or (II)

[0007]

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[Wherein R ¹ and R ² each independently represent an amino group, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms; Represents O, S or NH]. In R ¹ and R ² , examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, and a propyl group.
Examples of the aryl group having 20 to 20 include a phenyl group, and examples of the arylalkyl group having 7 to 20 carbon atoms include a benzyl group. Specific examples of aminotriazine compounds that can be suitably used include melamine, methylguanamine, benzoguanamine, benzylguanamine, 2,4-diamino-6-morpholino-1,
3,5-triazine, 2,4-diamino-6-piperidino-1,3,5-triazine, 2,4-diamino-6
Thiomorpholino-1,3,5-triazine and the like;
These can be used alone or in combination. Particularly preferred is melamine. These aminotriazine compounds preferably have an average particle size of 0.1 to 50 μm, but are not limited to this particle size range.

The sulfuric acid to be reacted with the above-mentioned aminotriazine compound 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. However, it is preferable to use diluted sulfuric acid from the viewpoint of handling. The reaction ratio between the aminotriazine compound and sulfuric acid is 1: 0.1 to molar ratio.
1, preferably 1: 0.2 to 0.8. The molar ratio of sulfuric acid is
If it is less than 0.1, the effect of imparting water resistance to the aminotriazine compound is low, which is not preferable. On the other hand, when the molar ratio of sulfuric acid is larger than 1, unreacted sulfuric acid tends to remain, so that a large amount of washing is required, which is not preferable. The method of reacting the aminotriazine compound with sulfuric acid is not particularly limited, and a conventionally known method can be used. For example,
A method in which sulfuric acid is added little by little or at a time at room temperature with the aminotriazine compound previously dispersed in water, a method in which sulfuric acid is added with stirring while the aminotriazine compound is pulverized at room temperature with a ball mill, etc. A method of adding the compound is exemplified. The reaction conditions are not particularly limited, and the reaction may be performed at a normal temperature, and the pressure may be any of reduced pressure, normal pressure, and increased pressure.

The flame-retardant resin composition of the present invention contains 50 to 90 parts by weight of the component (A) and 10 to 50 parts by weight, preferably 20 to 40 parts by weight, of the component (A). )) And 100 parts by weight. When the amount of the sulfate of the aminotriazine compound (B) is less than the above lower limit, the light resistance is poor (ΔE is 1 or more), and a sufficient flame retardant effect is not obtained (flame retardant performance V−). 2 is not obtained), and when it is more than the upper limit, the light resistance is good (ΔE is less than 1), but a sufficient flame retardant effect is not obtained (flame retardant performance V-2 is not obtained). ),
Moldability and impact resistance are reduced, and furthermore, the use of a large amount of a sulfate of an aminotriazine compound increases the cost, which is not preferable. In addition, the said flame retardant performance was measured by the vertical combustion test according to UL standard.

The flame-retardant resin composition of the present invention may contain, if necessary, a conventionally known antioxidant (for example, a phenolic compound or a phenolic compound) in addition to the above components, as long as the object of the present invention is not impaired.
Phosphorus compounds, sulfur compounds, etc.), weathering agents (benzophenones, salicylates, benzotriazoles, hindered amines, etc.), metal deactivators, coloring agents, antistatic agents (anionic, cationic, nonionic, Amphoteric), lubricant (fatty acid, fatty acid amide, fatty acid metal salt, fatty acid ester, hydrocarbon type, etc.), nucleating agent (metal salt type, sorbitol type, etc.), filler (talc, calcium carbonate, barium sulfate, glass fiber, Mica, etc.), a blooming inhibitor and the like.

The resin composition of the present invention can be produced by melt-kneading the above-mentioned components by any method. For example, there is a method using a high-speed stirrer represented by a Henschel mixer, a single-screw or twin-screw continuous kneader, a roll mixer or the like, alone or in combination. The molding method of the resin composition thus obtained includes:
There is no particular limitation, and there are methods such as injection molding, extrusion molding, and blow molding, but injection molding is particularly preferred. The molded body thus obtained has the flame retardancy of V-2,
Xenon lamp irradiation 350 hours, black panel 63 ° C
When the light fastness test was performed under the condition of (1), the color difference (ΔE) was 1
And the yellowness (ΔYI) is less than 4, and has high light fastness.

[0013]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. The substances used in the following examples and comparative examples are as follows. 1) Polypropylene Idemitsu Polypro J400M (MI = 4.5 g / 10 min) Idemitsu Polypro J700G (MI = 10.0 g / 10 min) Idemitsu Polypro J900GP (MI = 16.6 g / 10 min) Idemitsu Polypro J 2000GP (MI = 20 min) 0.2 g / 10 min) Idemitsu Polypro J 3000 GP (MI = 31.2 g / 10 min) Idemitsu Polypro H 700 (MI = 10.5 g / 10 min) 2) Propylene-ethylene block copolymer Idemitsu Polypro J450HP (MI = 4 Idemitsu Polypro J650HP (MI = 7.0 g / 10 min) Idemitsu Polypro J950H (MI = 19.7 g / 10 min) Idemitsu Polypro J3050H (MI = 31.6 g / 10 min) Idemitsu Polypro J5053H (MI = 55.0 g / 10 min) Idemitsu Polypropylene B 780 (MI = 17.9 g / 10 min) MI value of the polyolefin used is a blend of different polyolefins having MI values, since the relationship between the composition and the MI is a linear relationship (semi-log) was calculated by interpolating the composition obtained by blending. 3) Melamine sulfate manufactured by Sanwa Chemical Co., Ltd., trade name: Avinone 901 Average particle size: 11.4 μm 4) Benzoguanamine sulfate and 2,4-diamino-6
Synthesis of morpholino-1,3,5-triazine sulfate 5 mol of benzoguanamine or 2,4-diamino-6-morpholino-1,3,5-triazine having an average particle diameter of 30 μm is dispersed in 1 liter of water at room temperature. Sulfuric acid with stirring
2.5 moles (concentration 40% by weight) were added slowly. After reacting for 1 hour, the mixture was filtered to obtain benzoguanamine sulfate or 2,4-diamino-6-morpholino-1,3,5-triazine sulfate. Subsequently, it was washed with water and dried.

Examples 1 to 11 and Comparative Examples 1 to 4 Premix A polyolefin having a composition and a compounding amount shown in Table 1 was mixed with
The aminotriazine compound sulfates shown in the table and 0.2 parts by weight of tris (2,4
-Di-t-butylphenyl) phosphite (MARK2112 manufactured by Asahi Denka Co., Ltd.) and 0.1 part by weight of pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-hydroxyphenyl) propionate (chiba- Geigy I
RGANOX1010) and 0.3 parts by weight of calcium stearate (manufactured by Dainippon Ink and Chemicals, Inc.) were blended and premixed with a Henschel mixer or tumbler. Melt kneading The obtained preliminary mixture is heated to 160 ° C. to 240 ° C. by using a twin-screw kneader (trade name: PCM45II manufactured by Ikegai Iron and Steel Co., Ltd.).
To prepare a composition, and pelletized using a strand cut. The composition pellets thus obtained,
Injection molding machine (trade name: FE-12) manufactured by Nissei Plastic Industry Co., Ltd.
0, PS-40), cylinder temperature 190-21
Injection molding is performed at 0 ° C. and a mold temperature of 50 ° C. to produce a test piece.
The characteristics were evaluated by the following evaluation methods, and the results are shown in Table 2.

Flame retardancy evaluation (UL94) Test machine: HVUL plastic UL combustion test chamber manufactured by Atlas Co., Ltd. Test method: For a test piece having a thickness of 1/16 inch, UL9
A vertical combustion test was performed according to Example 4. Measurement of MI Test machine: Melt indexer S-001, manufactured by Toyo Seiki Seisaku-sho, Ltd. Test method: Measured at 230 ° C. and 2.16 kg. Light fastness tester: Atlas Electric Devices (AT
LAS ELECTRIC DEVICESCO.) WEATHER OMETER, Model C16
5 Test method: Irradiation was performed for 350 hours with a xenon lamp under conditions of a black panel at 63 ° C. and a humidity of 50%. ΔE and ΔYI Measurement Testing Machine: SM Color Computer SM-3 manufactured by Suga Test Instruments Co., Ltd. The ΔE and ΔYI were measured.

[0016]

[Table 1]

[0017]

[Table 2]

[0018]

[Table 3]

[0019]

[Table 4]

[0020]

According to the present invention, since there is no remarkable color, toning is easy, and there is no decrease in mechanical strength.
It is possible to provide a resin composition having high flame retardancy (V-2 according to UL94), excellent light resistance, high flowability, and suitable for injection molding, and a molded product thereof. In addition, the resin composition of the present invention and the molded product thereof emit little smoke even during combustion, do not generate harmful gas, and have no flying matter.
Therefore, the resin composition of the present invention is useful for various applications of currently used polyolefins, and includes, for example, exterior materials (housing and the like) requiring flame retardancy, such as home electric appliances, OA products, and automobiles. It is suitable for molding interior parts (connectors, substrate holders, etc.).

Claims (6)

[Claims] (A) 50 to 90 parts by weight of a polyolefin resin having a melt index of 7 to 100 g / 10 min at a temperature of 230 ° C. and a load of 2.16 kg; and (B) 10 to 50 parts by weight of a sulfate of an aminotriazine compound. A flame-retardant resin composition comprising: (A) a component and (B) a total amount of 100 parts by weight. 2. The polyolefin resin of the component (A),
The flame-retardant resin composition according to claim 1, which is polypropylene. 3. The polyolefin resin of the component (A),
The flame-retardant resin composition according to claim 1, which is a mixture of polypropylene and a propylene-ethylene block copolymer. 4. The sulfate of the aminotriazine compound as the component (B) is represented by the general formula (I) or (II): [Wherein, R ¹ and R ² each independently represent an amino group, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms; S or NH]. The flame-retardant resin composition according to claim 1, which is a sulfate of an aminotriazine compound represented by the formula: 5. The flame-retardant resin composition according to claim 1, wherein the sulfate of the aminotriazine compound (B) is melamine sulfate. 6. A molded article comprising the flame-retardant resin composition according to any one of claims 1 to 5.