JPH11116744A - Flame-retardant resin composition and molded article made therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which gives a molded article excellent in mechanical properties and heat resistance and free from bleeding and which suffers neither scorching nor foaming during processing by blending a polyolefin resin, an amine salt made from an amine compound and pyrophosphoric acid or condensed phosphoric acid, and a hydroxylated compound each in a specified amount. SOLUTION: This composition consists of a polyolefin resin (A) preferably comprising PP, an amine salt (B) which is made from an amine compound containing at least one N atom, preferably comprising melamine, benzoguanamine or 1,2-diaminoethane, more preferably melamine, and pyrophosphoric acid or condensed phosphoric acid, and a hydroxylated compound (C) preferably comprising dipentaerythritol or a product of reaction of adipic acid with dipentaerythritol, wherein the content of component A is 40-90 wt.%, the total content of component Band component C is 60-10 wt.%, and the weight ratio of component 13 to component C is (1 to 30):1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition and a molded product thereof, and more particularly to an injection molded product, an extruded cable, insulation and coating of a wire, an extruded and calendered sheet, and an extruded product. It is useful for molding blow-molded products such as members and pins. In particular, exterior materials (such as housings) and internal parts (connectors, board holders, etc.) that require flame retardancy in home electric appliances, OA products, automobiles, etc. )Such,
The present invention relates to a flame-retardant resin composition useful for molding a molded article made of a flame-retardant polyolefin material, 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. But,
It has been pointed out that when the compounded resin is burned or exposed to high heat, harmful and toxic gases 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-53-92855 and JP-A-54-29350 disclose flame-retardant resin compositions in which a water-containing inorganic compound such as aluminum hydroxide or magnesium hydroxide is blended as a flame retardant. I have. However, a large amount of a water-containing inorganic compound must be added to impart high flame retardancy, and a composition to which a large amount of a water-containing inorganic compound is added has some problems in processability, mechanical properties, and the like. In addition, there is a problem that the appearance of the molded article is deteriorated. Also, JP-A-60-36542 discloses that
A flame-retardant resin composition in which a polyhydric alcohol is used in combination with ammonium polyphosphate is disclosed. However, this composition has sufficient flame retardancy, but has poor heat resistance, so that there is a problem that stagnant burning or foaming occurs in a molding machine, and thus the appearance of a molded product is deteriorated. There is also a problem that bleed-out occurs on the surface of the molded product.

[0004]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and does not reduce light resistance.
High flame retardancy with low added flame retardant (UL-94, 1/3
2 inches, V-0), without deteriorating the mechanical properties of the molded product, and has good heat resistance, so there is no burning or foaming during processing, and there is no bleed-out in the molded product. For this reason, it is possible to obtain molded products with good appearance, and because it uses non-halogen flame retardants, it generates harmful and toxic gases and smokes and does not corrode molding machines. It is an object to provide a product and a molded product thereof.

[0005]

The inventors of the present invention have conducted intensive studies and found that an amine salt of an amine compound containing at least one nitrogen atom, an amine salt of pyrophosphoric acid or condensed phosphoric acid, a hydroxyl group, The present inventors have found that the above object can be achieved by blending a contained compound in a specific amount, thereby completing the present invention. That is, the present invention comprises (A) a polyolefin resin, (B) an amine compound containing at least one nitrogen atom, an amine salt of pyrophosphoric acid or condensed phosphoric acid, and (C) a hydroxyl group-containing compound,
The component (A) is 40 to 90% by weight and the total of the component (B) and the component (C) is 60 to 10% by weight, and the compounding ratio of the component (B) to the component (C) is 1 to 30 by weight. And a molded article obtained by molding the composition.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the resin composition of the present invention,
Examples of the polyolefin resin (A) include a polypropylene resin, a polyethylene resin, a polybutene resin, and a polypentene resin. Examples of the polypropylene resin include propylene homopolymer (polypropylene) and propylene. A copolymer as a component is exemplified.

The above-mentioned copolymer includes, for example, a propylene / α-olefin copolymer, and the α-olefin includes, for example, ethylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-butene, 1-
Penten and the like.

Examples of the polyethylene resin include an ethylene homopolymer (polyethylene) and a copolymer containing ethylene as a main component.

Examples of the copolymer include ethylene / α-olefin copolymers, and examples of the α-olefin include 1-hexene, 4-methyl-1-pentene, 1-octene and 1-octene. Butene, 1-pentene and the like.

Other polyolefin resins include, for example, ethylene / vinyl acetate copolymer and ethylene / ethyl acrylate copolymer.

The polyolefin resin used in the present invention may be a mixture of the above polyolefin resins. In the present invention, polypropylene is particularly preferred.

The amine salt of component (B) includes 1,2-
Diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, urea, N, N′-dimethylurea, thiourea, isocyanuric acid, ethylene urea , Ethylenethiourea, hydantoin, hexahydropyrimidin-2-one, parabanic acid, valpituric acid, ammeline, melon,
Melam, guanazole, guanazine, guanidine, ethyleneimine, pyrrolidine, 2-pyrrolidone, 3-pyrrolidone, piperidine, morpholine, thiomorpholine, α-
Piperidone, β-piperidone, γ-piperidone, piperazine, 4-methylpiperazine, 2-methylpiperazine,
2,5-dimethylpiperazine, 2,3,5,6-tetramethylpiperazine, 2-ethylpiperazine, 2,5-diethylpiperazine, melamine, guanamine, methylguanamine, ethylguanamine, benzoguanamine, benzylguanamine, dicyandiamide, 1, 3-diaminobenzene, 1,4-diaminobenzene, 2,4-diaminotoluene, 2,4-diamino-6-morpholino-1,3,5
-Pyrrophosphate or condensed phosphate such as triazine, 2,4-diamino-6-thiomorpholino-1,3,5-triazine [herein, condensed phosphoric acid is polyphosphoric acid in which three or more phosphoric acids are condensed. Acids (triphosphoric acid, tetraphosphoric acid, condensates of more phosphoric acid, or a mixture thereof, and are mainly linear but may have a branched structure)] and the like. No. These can be used alone or as a mixture.

Specific examples of amine salts which can be suitably used include melamine, methylguanamine, benzoguanamine, 2,4-diamino-6-morpholino-1,3,5-
Pyrophosphates or condensed phosphates such as triazine, 1,2-diaminoethane, 1,6-diaminohexane, ethylene urea, guanazine, guanidine, etc., and particularly preferably melamine, benzoguanamine, and pyrroline of 1,2-diaminoethane Acid salts or condensed phosphates.

These amine salts are described in JP-B-6-8308.
No. 4,599,375, and the like. A resin composition in which an amine salt composed of orthophosphoric acid (in which phosphoric acid is not condensed) is blended in place of the component (B), foams during melt-kneading, injection molding, extrusion molding, etc., and is difficult to process. Becomes

As the hydroxyl group-containing compound of the component (C),
Pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, sorbitol, glucose, mannitol, cellulose,
Glucose, xylitol, glycerin, trishydroxyethyl isocyanurate, polyethylene glycol,
Polyvinyl alcohol, bisphenol A, reaction product of adipic acid and pentaerythritol, reaction product of adipic acid and dipentaerythritol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,
4,8,10-tetraoxaspiro [5,5] undecane, epoxy resin, phenol resin, phenoxy resin,
Examples thereof include polyvinyl butyral, polyhydroxy polyolefin, cellulose, cellulose derivatives, and wood flour. Powders of metal complex salts of these hydroxyl-containing compounds and boric acid [synthesized by adding a water-soluble metal salt (such as zinc acetate) or a metal carbonate to a reaction product of the hydroxyl-containing compound and boric acid] Comb-shaped polymer compound comprising a polyethylene main chain and a polyoxyalkylene side chain (compound obtained by graft-polymerizing ethylene oxide onto a saponified ethylene-vinyl acetate copolymer: JP-A-3-22
7307) and the like. These can be used alone or as a mixture.

Specific examples of the hydroxyl group-containing compound that can be suitably used include dipentaerythritol, polyethylene glycol, a reaction product of adipic acid and dipentaerythritol, a phenol resin, an epoxy resin, and zinc borate of dipentaerythritol. A complex salt, a comb-shaped polymer compound comprising a polyethylene main chain and a polyoxyalkylene side chain. Particularly preferred are dipentaerythritol and reaction products of adipic acid and dipentaerythritol. The amount of the component (A) in the composition of the present invention is 4
The content is 0 to 60% by weight, preferably 50 to 80% by weight.

(B) in the flame-retardant resin composition of the present invention
The compounding amount of the component and the component (C) is 60 to 10% by weight in total of the component (B) and the component (C), but is preferably 50 to 20% by weight. When the amount is more than 60% by weight, the light resistance is good (ΔE is less than 3), but a sufficient flame-retardant effect is not obtained (flame-retardant performance V-0 is not obtained). The appearance is impaired, the mechanical properties are reduced, and a large amount of flame retardant is used, resulting in high costs. If the amount is less than 10%, a sufficient flame retardant effect (flame retardant performance V-
0) and good light fastness cannot be obtained. The blending ratio of the components (B) and (C) [(B) / (C)] is 1 by weight.
It must be ~ 30, preferably 2-10. If the compounding ratio is less than 1, a sufficient flame-retardant effect cannot be obtained (flame-retardant performance V-0 cannot be obtained). If the compounding ratio is less than 1, the component (C) is mixed more than the component (B). Therefore, bleed out occurs in the molded product, heat resistance decreases, burning or foaming occurs during processing, mechanical properties decrease, and the appearance and light resistance of the molded product deteriorate (ΔE is 3 or more). The mixing ratio is 3
If it exceeds 0, a sufficient flame retardant effect (flame retardant performance V-0) cannot be obtained.

The flame-retardant resin composition of the present invention may further contain, in addition to the above-mentioned components, fillers, lubricants, and antioxidants which are usually blended with the resin composition as needed, as long as the object of the present invention is not impaired. Agents, antistatic agents, ultraviolet absorbers and the like can be appropriately compounded.

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 and blow molding, but injection molding is particularly preferred. Products obtained by injection molding can be used for applications in the field of polyolefins currently in use, especially in home appliances, O
It is suitable for applications such as A products, exterior materials (such as housings) and internal parts (connectors, board holders, etc.) that require flame retardancy in the automotive field, etc.

[0020]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The substances used in the following examples and comparative examples are as follows. 1) Polypropylene Idemitsu Polypro J700G (MI = 10.0 g / 10 min) 2) Propylene-ethylene block copolymer Idemitsu Polypro J650HP (MI = 7.0 g / 10 min) Idemitsu Polypro B-780 (MI = 17.9 g / min) The MI value of the polyolefin used was measured using a tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., melt indexer S-00).
The measurement was performed under the conditions of 230 ° C. and 2.16 kg using 1). 3) Melamine pyrophosphate manufactured by Mitsui Toatsu Fine Co., Ltd. Average particle size: 5-6 μm 4) Melamine phosphate manufactured by Sanwa Chemical Co., Ltd., P7202 Average particle size: 10 μm or less 5) Melamine polyphosphate manufactured by Sanwa Chemical Co., Ltd. 6) Ammonium polyphosphate, Hoechst Co., Ltd., AP-422, average particle size 15 μm 7) Dipentaerythritol, Koei Chemical Co., Ltd., dipentalit 8) Adipic acid and dipenta Reaction product with erythritol Ajinomoto Co., Ltd., Pren riser ST-210 9) Talc Asada Flour Milling Co., Ltd., JA-24RK Average particle size 2-4 μm 10) GF Nittobo Co., Ltd., 3J254S

Examples 1 to 10 and Comparative Examples 1 to 7 (1) Premixing Polyolefin, amine salt, hydroxyl group-containing compound, etc. having the composition and blending amount shown in Table 1 and 100 parts by weight of the total amount thereof 0.5 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (MARK21 manufactured by Asahi Denka Co., Ltd.)
12), 0.5 parts by weight of pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-hydroxyphenyl) propionate (IRGANO manufactured by Ciba-Geigy)
X1010) 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. (2) Melt kneading The obtained preliminary mixture was kneaded at 160 to 240 ° C. using a twin-screw kneader (trade name: PCM45II manufactured by Ikegai Iron and Steel Co., Ltd.) to prepare a composition, and then the strand cut was performed. Pelletized. The thus obtained composition pellets were injected into an injection molding machine (trade name: FE-120, manufactured by Nissei Resin Industry Co., Ltd.).
Cylinder temperature of 190 to 210 using PS-40)
A test piece was prepared by injection molding at 50 ° C. and a mold temperature of 50 ° C., and its characteristics were evaluated by the following evaluation methods. The results are shown in Table 1.

(1) Flame retardancy evaluation (UL94) Testing machine: HVUL plastic UL combustion test chamber manufactured by Atlas Co., Ltd. Test method: 1/32 inch thickness of test piece, UL9
A vertical combustion test was performed according to Example 4. (2) Izod impact strength Measured according to ASTM D256. (3) Flexural strength Measured according to ASTM D790. (4) Tensile strength Measured according to ASTM D638. (5) Evaluation of Retention Burn during Injection Molding The composition was retained in a cylinder at 220 ° C. for 5 minutes, then injection molded, and the degree of burn on the surface of the molded product was evaluated according to the following criteria. ：: No burning △: Burning (6) Evaluation of foaming during injection molding The composition was retained in a cylinder at 220 ° C. for 5 minutes, then injection molded, and the degree of foaming due to decomposition of the surface of the molded product Was evaluated according to the following criteria. ：: No foaming ×: Foaming (7) Bleed-out property of molded product surface The presence or absence of exudate (flame retardant etc.) on the molded product surface was visually evaluated according to the following criteria. ○: No stickiness or abnormality on the surface ×: No stickiness or abnormality on the surface (8) Light fastness test machine: Atlas Electric Devices (AT
LAS ELECTRIC DEVICESCO.) Weather Ometer (WEA
THER OMETER), Model CI65 Test Method: Irradiated with a xenon lamp for 350 hours under conditions of black panel 63 ° C. and humidity 50%. (9) ΔE measurement Test machine: SM color computer SM-3ΔE manufactured by Suga Test Instruments Co., Ltd. was measured. (10) Appearance of Molded Article Visually evaluated according to the following criteria. <Hue> ○: No coloring ×: Coloring <Surface smoothness> ○: Smooth ×: Rough

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

[Table 3]

As is clear from Table 1, Examples 1 to 1
The molded article obtained by molding the composition No. 0 has excellent flame retardancy, tensile properties, bending properties and impact resistance, and is free from burning and foaming, has excellent heat resistance, and further has bleed-out resistance. Excellent light fastness and product appearance. On the contrary,
A molded article of the composition (Comparative Example 1) in which the total amount of melamine polyphosphate and dipentaerythritol is less than 10% by weight has poor flame retardancy and light resistance. A molded article of the composition (Comparative Example 2) in which the total amount of melamine polyphosphate and dipentaerythritol exceeds 60% by weight is excellent in light resistance, but slightly inferior in flame retardancy, and has tensile properties, bending properties and resistance to heat. Poor impact, burning or foaming during molding, poor bleed-out resistance, poor appearance of molded product. A molded article of a composition (Comparative Example 3) in which the ratio of melamine polyphosphate to dipentaerythritol (melamine polyphosphate / dipentaerythritol) exceeds 30 has poor flame retardancy. A molded article of a composition (Comparative Example 4) containing neither dipentaerythritol nor the reaction product of adipic acid and dipentaerythritol was obtained.
Poor flame retardancy. A molded article of a composition (Comparative Example 5) in which the ratio of melamine polyphosphate to dipentaerythritol is less than 1 has slightly poor flame retardancy and all other properties are poor. The composition (Comparative Example 6) in which melamine phosphate was blended in place of melamine polyphosphate in the formulation of Example 1 foamed significantly during melt-kneading, vented up, and significantly foamed in the retention burn evaluation in injection molding. did. Further, the flame retardancy of the molded article is excellent, but all other properties are poor. The molded article of the composition (Comparative Example 7) in which ammonium polyphosphate was blended in place of melamine polyphosphate in the blend of Example 1 bleeds out violently from the surface and has excellent flame retardancy. All physical properties are bad.

[0027]

According to the present invention, a high flame retardancy (UL-9) can be obtained with a low amount of a flame retardant without a decrease in light resistance.
4, 1/32 inch, V-0),
Since the heat resistance is good without lowering the mechanical properties of the molded product, there is no burning or foaming at the time of processing, there is no bleed-out in the molded product, and therefore, a molded product having a good appearance can be obtained. Since a non-halogen flame retardant is used, it is possible to provide a flame-retardant resin composition and a molded article thereof that do not generate harmful and toxic gases and smoke and do not corrode molding machines.

Claims (5)

[Claims] 1. A polyolefin resin comprising: (A) an amine salt of at least one nitrogen atom-containing amine compound with pyrophosphoric acid or condensed phosphoric acid; and (C) a hydroxyl group-containing compound, Component 40-90% by weight, the total of component (B) and component (C) is 60-10% by weight, and the compounding ratio of component (B) to component (C) is 1-30 by weight. Flammable resin composition. 2. The polyolefin resin of the component (A),
The flame-retardant resin composition according to claim 1, which is polypropylene. 3. The flame-retardant resin composition according to claim 1, wherein the amine salt of the component (B) is melamine pyrophosphate or melamine condensed phosphate. 4. The flame-retardant resin composition according to claim 1, wherein the hydroxyl group-containing compound as the component (C) is dipentaerythritol or an adipic acid-dipentaerythritol reaction product. 5. A molded article obtained by molding the resin composition according to any one of claims 1 to 4.