JP2855457B2 - Flame retardant resin composition - Google Patents

Description

The present invention relates to a flame-retardant resin composition having flame retardancy and excellent weather resistance.

[Related Art] Recently, thermoplastic resins have been widely used for automobile parts, home electric parts, office parts, industrial parts, miscellaneous goods, and the like. In addition, materials having flame retardancy have been required.

As the flame retardant, various inorganic flame retardants and organic flame retardants are known, and halogen-based organic flame retardants have hitherto been widely used for making a thermoplastic resin flame-retardant. However, since the flame-retardant composition of a thermoplastic resin generates a large amount of corrosive halogen-containing gas when burned, a non-halogen flame retardant must be used when this becomes a problem.

Hydrous inorganic compounds such as magnesium hydroxide and aluminum hydroxide are used as non-halogen flame retardants, but they need to be added in large amounts to the resin, which has the drawback that the mechanical properties are greatly reduced. Also, apart from these hydrous inorganic compounds, ammonium polyphosphate and 1,1
It is known that a system comprising a 3,5-triazine derivative is useful as a flame retardant for a thermoplastic resin (Japanese Patent Laid-Open No.
No. 147050, JP-A-1-193347).

However, ammonium polyphosphate and 1,1
Although the composition to which the 3,5-triazine derivative is added has excellent flame retardancy, it is easily deteriorated by the action of light (or ultraviolet rays) particularly under rainy conditions, and has a disadvantage that it is cheap. ing.

[Problems to be Solved by the Invention] Under such circumstances, the present invention has been made to solve the above-mentioned drawbacks of the prior art, and an object of the present invention is to provide excellent flame retardancy and weather resistance. It is to provide a flame-retardant resin composition having excellent heat resistance.

[Means for Solving the Problems] The present invention provides: (a) 55 to 86.7 parts by weight of a thermoplastic resin, (b) ammonium polyphosphate or polyphosphoramide.
10 to 25 parts by weight, (c) the following general formula (I) [In the formula, X represents a morpholino group or a piperidino group, Y represents a divalent group of piperazine, and n is an integer of 2 to 50. 1,3,5-triazine derivative 3 having a structure represented by the following formula:
A flame-retardant resin composition characterized by containing 0.3 to 10 parts by weight and (d) 0.3 to 10 parts by weight of a polyorganosiloxane, which solves the above-mentioned problems of the prior art.

 Hereinafter, the present invention will be described in detail.

The thermoplastic resin (a) used for producing the flame-retardant resin composition of the present invention includes polyethylene, polypropylene, polybutene-1, and poly-4-methyl-pentene-1.
Such as polyolefins and copolymers thereof, polystyrene, polyamide, ionomer, polyurethane, ethylene-acrylate copolymer, polyvinyl chloride, styrene-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, polyphenylene oxide , Polyphenylene oxide-polystyrene mixture or copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-butene-
And a mixture of 1 copolymer and the above-mentioned thermoplastic resin.

The mixing ratio of the thermoplastic resin is 55 to 8 with respect to the resin composition.
It is 6.7 parts by weight, preferably 61 to 84 parts by weight.

If the compounding ratio exceeds 86.7 parts by weight, satisfactory flame retardancy cannot be obtained, and if the compounding ratio is less than 55 parts by weight, only the mechanical properties are greatly reduced.

As (b) ammonium polyphosphate or polyphosphoramide used in the present invention, commercially available products are usually used as they are. As the commercially available product, for example, Sumisafe P (trade name:
Sumitomo Chemical Co., Ltd.), Sumisafe PM (trade name: Sumitomo Chemical Co., Ltd.), Exolit 263 (trade name: Hoechst), Phos-Check P130 (trade name: Monsanto Chemical Company) And the like. The compounding ratio of the ammonium polyphosphate or polyphosphoramide is 10 to 25 parts by weight, preferably 11 to 23 parts by weight, based on the resin composition. If the compounding ratio is less than 10 parts by weight, satisfactory flame retardancy cannot be achieved, and if it is more than 25 parts by weight, no further improvement in flame retardancy can be obtained, which only leads to a decrease in mechanical properties and a high cost. It is.

As the (3) 1,3,5-triazine derivative (c) used in the present invention, it is preferable to use the compounds disclosed in JP-A-59-147050 and JP-A-1-193347, and 2-piperazinylene-4-morpholino Examples thereof include oligomers or polymers of 1,3,5-triazine and oligomers or polymers of 2-piperazinylene-4-piperidino-1,3,5-triazine.

The compounding ratio of the 1,3,5-triazine derivative is 3 to 10 parts by weight, preferably 4 to 8 parts by weight, based on the resin composition. If the compounding ratio is 3 parts by weight or less, satisfactory flame retardancy cannot be achieved, and even if 10 parts by weight or more is added, no further improvement in flame retardancy can be obtained.

Next, the silicone compound (d) used in the present invention is a polyorganosiloxane, which is generally a compound classified into silicone oil, silicone rubber or silicone resin based on its properties (for example, “Silicone and its applications”, Toshiba Described in Silicone Co., Ltd.).

The mixing ratio of the polyorganosiloxane is from 0.3 to 10 parts by weight, preferably from 0.5 to 8 parts by weight, based on the resin composition. If the polyorganosiloxane is not blended, the resin composition is degraded in a short period of time under light (or ultraviolet), especially under rainy conditions, and becomes difficult to use. However, the incorporation of the polyorganosiloxane surprisingly significantly improves the weather resistance. If the compounding ratio is 0.3 parts by weight or less, the effect of improving the weather resistance is unsatisfactory.

In the present invention, in order to further improve the weather resistance of the flame-retardant resin composition, it is preferable to further compound a hindered amine compound.

Examples of hindered amine compounds include bis- (2,2,6,6-tetramethyl-4-piperidyl)
Sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, dimethyl-1- (2-hydroxyethyl) succinate-
2,2,6,6-tetramethyl-4-hydroxypiperidine polycondensate, poly [(6-morpholino-S-triazine-2,4-diyl)} (2,2,6,6-tetramethyl-4 -Piperidyl)
Imino {-hexamethylene} (2,2,6,6) -tetramethyl-4-piperidyl) imino}], poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3 , 5-Triazine-2,4-diyl {2,2,6,6-tetramethyl-4-piperidyl) imino {hexamethylene} (2,2,6,6-tetramethyl-4-piperidyl) imino} Bis (1,2,2,6,6-pentamethyl-4-piperidyl) 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, tetrakis (2 , 2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,1 '-(1,2-ethanedale) bis (3,3,5,5-tetra Methylpiperazino), N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and a polycondensate of 1,2-dibromoethane, and the following structural formula Mark LA-6, which is
2, Mark LA-63, Mark LA-67, Mark LA-68 (ADEKA
Argus Chemical Co., Ltd.), and the like, but are not limited thereto.

Mark LA-62 (molecular weight about 900); Wherein R ₁ , R ₂ , R ₃ and R ₄ are each C ₁₃ H ₂₇ — or the following formula (A) Represents a group represented by Mark LA-63 (molecular weight about 2000); [Wherein, R represents —CH ₃ , Q is the following formula (B) Represents a group represented by Mark LA-67 (molecular weight about 900); Wherein R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each C ₁₃ H ₂₇ −
Or the following formula (C) Represents a group represented by Mark LA-68 (molecular weight about 1900); [Wherein Q and BTC represent the same meaning as described above. The hindered amine compound is a flame retardant resin composition 10
0.01 to 1.0 part by weight, preferably 0.03 to 0.
5 parts by weight are blended. If the amount is less than 0.01 part by weight, the effect of improving the weather resistance cannot be obtained. On the other hand, if the amount is more than 1.0 part by weight, it is not only uneconomical but also causes problems such as bleeding and deterioration of appearance.

In order to further improve the flame retardancy and weather resistance of the flame retardant resin composition of the present invention, it is preferable to use a phenolic antioxidant in combination.

Examples of preferred phenolic antioxidants include 2,6-di-t-butyl-4-methylphenol, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate ], 1,6-hexanediol-bis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate, 2,2-thiobis (4-methyl-6-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-t-
Butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4'-butylenebis (3-methyl-6-tert-butylphenol), 4, 4'-thiobis (3-methyl-6-t-butylphenol), 2,2-methylenebis (4-methyl-6-t-butylphenol), tris- (2-methyl-4-hydroxy-5-t-butylphenyl) ) Butane, 2,2'-ethylidenebis (4,6-di-t-butylphenol), 2-t-butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl)- 4-methylphenyl acrylate, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy}-
1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, N, N'-hexamethylenebis (3,5-di-t-butyl-
4-hydroxy-hydrocinnamamide), N, N'-bis [3- (3,5-di-tert-dibutyl-4-hydroxyphenyl) propionyl] hydrazine, 2,2'-oxaamidobisethyl-3 -(3,5-di-t
-Butyl-4-hydroxyphenyl) propionate and the like.

The addition amount of these phenolic antioxidants is 0.01 to 1.0 part by weight, preferably 0.03 to 0.5 part by weight, per 100 parts by weight of the flame retardant resin composition.

It is preferable to use an ultraviolet absorber in combination with the composition of the present invention because the weather resistance is further improved.

Examples of the ultraviolet absorber include hydroxybenzophenones such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-stearyloxybenzophenone, and 2-hydroxy-4-dotesiloxybenzophenone. Phenyl salicylate, n-hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-butyl-phenyl-3,5-di-tert-butyl-4'-hydroxy Benzoate, 4-octylphenyl-3,5-di-t-butyl-4-
Benzoates such as hydroxybenzoate, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy -5'-octylphenyl)
Benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2' -Hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-
Benzotriazoles such as methylphenyl) -5-chlorobenzotriazole and 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole.

The amount of addition of these ultraviolet absorbers depends on the flame retardant resin composition 10
0.01 to 1.0 part by weight, preferably 0.03 to 0.
5 parts by weight.

Also, 2 ', 2'-thiobis (4-t-octylphenol) nickel salt, [2,2'-thiobis (4-t-octylphenolate)]-n-butylamine nickel salt, (3,5-di- t-butyl-4-hydroxybenzyl)
The addition of nickel compounds such as phosphonic acid monoethyl ester nickel salt improves weather resistance.

It is preferable to use a phosphorus-based antioxidant in combination with the flame-retardant resin composition of the present invention since the weather resistance is further improved.

Examples of the phosphorus-based antioxidant include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, triphenyl phosphite, and tris (nonylphenyl) ) Phosphite, distearylpentaerythritol diphosphite, tris (3,5-di-t-butyl-4-hydroxyphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite , Bis (2,6-di-t-butyl-4-methylphenyl)
Pentaerythritol diphosphite, tris [4,4'-isopropylidenebis (2-t-butylphenol)] phosphite, di (nonylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) ) -4,4 '
-Bisphenylenediphosphonite and the like.

The addition amount of these phosphorus-based antioxidants depends on the flame-retardant resin composition.
0.001 to 1 part by weight, preferably 0.01 to 1 part by weight, per 100 parts by weight
0.5 parts by weight.

Further, it is preferable to use a sulfur-based antioxidant in combination, because the flame retardancy is improved.

Examples of the sulfur-based antioxidant include dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate-
Polyalkyl alcohols of alkylthiopropionic acids such as butylthiopropionic acid, octylthiopropionic acid, laurylthiopropionic acid, stearylthiopropionic acid (eg, glyceryl, trimethylolethane, trimethylolpropane,
Esters of pentaerythritol and trishydroxyethyl isocyanurate (for example, pentaerythritol tetrakis (dodecylthiopropionate) and pentaerythritol tetrakis (β-lauryl-thiopropionate)).

The addition amount of these sulfur-based antioxidants is 0.001 to 1.0 part by weight, preferably 0.01 part by weight, per 100 parts by weight of the flame-retardant resin composition.
1 to 0.5 parts by weight.

Other if necessary, the flame retardant resin composition of the present invention,
Engraving agent, metal soap, plasticizer, epoxy compound, pigment,
Fillers, foaming agents, antistatic agents, lubricants, other flame retardants that do not adversely affect weather resistance, processing aids, and the like can be included.

The flame-retardant resin composition of the present invention can be produced, for example, by the following method.

That is, a predetermined amount of the above-mentioned ammonium polyphosphate or polyphosphoric amide and a 1,3,5-triazine derivative and a silicone compound having a structure represented by the general formula (I) and the above-mentioned various additives are added to a thermoplastic resin.
For example, it can be obtained by stirring and mixing with a Hensiel mixer, a super mixer, a tumbler or the like, and then melt-kneading with a roll, a blender or the like, or kneading with a Banbury and then pelletizing.

[Examples] Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 Melt index 20 g / 10 minutes as polypropylene,
Ammonium polyphosphate (Sumisafe P, trade name: manufactured by Sumitomo Chemical Co., Ltd.) and 2-piperazinylene-4-morpholino as a 1,3,5-triazine derivative were added to a propylene-ethylene block copolymer having an ethylene content of 8% by weight. 1,3,
5-triazine polymer (n = 11), silicone compound (specifically, polyorganosiloxane; the same applies hereinafter), and 0.05% by weight of calcium stearate based on 100 parts by weight of the flame-retardant resin composition as various additives; Tetrakis [methylene-3- (3 ', 5'-di-t-butyl-
4-hydroxyphenyl) propionate] methane 0.15
Parts by weight, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, 0.05 parts by weight, were blended in the proportions shown in Table 1 and melt-kneaded and extruded at 220 ° C. using an extruder to obtain pellets. Was. Then, a flat plate having a thickness of 3 mm was prepared using an injection molding machine. From this flat plate, a 127 × 12.7 mm flammability test piece and a weather resistance test piece were cut out.

The flammability test was evaluated according to the method defined in UL standard UL94. The weather resistance test was performed using a sunshine weatherometer (black panel temperature: 83 ° C, spray cycle rain /
(Period: 18/120 minutes) The accelerated weathering test was performed, and the time until the appearance abnormality such as cracks occurred on the test piece surface was defined as the weathering time. The results are shown in Table 2.

Example 2 In Example 1, bis- (2,2,6,6-
0.10 parts by weight of tetramethyl-4-piperidyl) sebacate and 2- (2'-hydroxy-3'-tert-butyl-
0.1 part by weight of 5'-methylphenyl) -5-chlorobenzotriazole was further added to the silicone compound to give the first compound.
The procedure was performed in the same manner as in Example 1 except that the components were blended at the ratios shown in the table. The results are shown in Table 2.

Examples 3 and 4 The procedure of Example 2 was repeated, except that the amount and type of the silicone compound were changed. The results are shown in Table 2.

Comparative example 1 It carried out similarly to Example 1 except not adding a silicone compound. The results are shown in Table 2.

Comparative Example 2 The procedure of Example 2 was repeated except that no silicone compound was added. The results are shown in Table 2.

Example 5 The test piece of Example 1 was subjected to a weather resistance test using an ultraviolet carbon fade meter (black panel temperature: 83 ° C.). The time until cracks occurred in the test piece was 210 hours.

Comparative Example 3 The test piece of Comparative Example 1 was subjected to a weather resistance test using an ultraviolet carbon fade meter (black panel temperature: 83 ° C.). The time until cracks occurred in the test piece was 150 hours.

[Effects of the Invention] (a) 55 to 86.7 parts by weight of a thermoplastic resin, (b) ammonium polyphosphate or polyphosphoramide
10 to 25 parts by weight, (c) the following general formula (I) [In the formula, X represents a morpholino group or a piperidino group, Y represents a divalent group of piperazine, and n is an integer of 2 to 50. 1,3,5-triazine derivative 3 having a structure represented by the following formula:
The composition of the present invention containing from 10 to 10 parts by weight and (d) 0.3 to 10 parts by weight of a polyorganosiloxane is excellent in flame retardancy and weather resistance, and is used for automobile parts, home electric parts, office parts, industrial use. parts,
It can be widely used for various molded products such as miscellaneous goods.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ identification code FI C08K 3:32 5: 3492 5: 357) (58) Investigated field (Int.Cl. ⁶ , DB name) C08L 1/00- 101/14 C08K 3/00-13/08

Claims (1)

(57) [Claims] (1) 55 to 86.7 parts by weight of a thermoplastic resin; (b) ammonium polyphosphate or polyphosphoramide
10 to 25 parts by weight, (c) the following general formula (I) [In the formula, X represents a morpholino group or a piperidino group, Y represents a divalent group of piperazine, and n is an integer of 2 to 50. 1,3,5-triazine derivative 3 having a structure represented by the following formula:
A flame-retardant resin composition characterized by comprising: to 10 parts by weight, and (d) 0.3 to 10 parts by weight of a polyorganosiloxane.