JP2522948B2 - Flame retardant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a flame-retardant resin composition having flame retardancy and excellent weather resistance.

<Prior Art> Recently, thermoplastic resins have been widely used for outdoor parts such as automobile parts, household electric appliances parts, containers, miscellaneous goods, and fences. In the above applications, materials having not only physical properties but also excellent weather resistance and flame retardancy have been demanded.

A flame retardant has been used as a method for making a resin flame-retardant. Flame retardants include halogen atoms, phosphorus atoms,
It is well known that a compound containing a nitrogen atom is effective, and especially when a flame retardant containing a halogen atom is used in combination with antimony trioxide, there is a synergistic effect of flame retardancy, and a flame retardant containing chlorine or bromine is most effective. It has been widely used. However, it is known that when a resin containing a flame retardant containing a halogen atom is irradiated with light, particularly ultraviolet rays, the halogen of the flame retardant becomes a halogen radical, which attacks the resin and accelerates the deterioration of the resin.

It has been disclosed in JP-A-59-500099 that silicone and silicone resin exhibit flame retardancy when added to a thermoplastic resin. However, a composition obtained by adding silicone and a silicone resin to a thermoplastic resin is still unsatisfactory in flame retardancy, and when used outdoors, it has a drawback that it is easily deteriorated by the action of ultraviolet rays. As it is, it cannot be used for outdoor applications.

<Problems to be Solved by the Invention> Under such circumstances, the problems to be solved by the present invention, that is, the object of the present invention is to solve the above-mentioned drawbacks of the prior art, and to provide excellent physical properties and flame retardancy. It is intended to provide a flame-retardant resin composition having excellent properties, excellent weather resistance, and resistant to outdoor use.

<Means for Solving Problems> The present invention provides 100 parts by weight of a composition comprising a) thermoplastic resin 50 to 98 parts by weight b) silicone oil 1 to 30 parts by weight c) silicone resin 1 to 20 parts by weight On the other hand, a flame-retardant resin composition comprising 0.01 to 5.0 parts by weight of a hindered amine compound, which solves the above conventional problems.

 Hereinafter, the present invention will be described in detail.

The thermoplastic resin used for producing the flame-retardant composition of the present invention includes polyolefins such as polyethylene, polypropylene, polybutene-1, and poly-4-methyl-pentene-1 and copolymers thereof, polystyrene, Polyamide, ionomer, polyurethane, ethylene-acrylic acid ester copolymer, polyvinyl chloride, styrene-butadiene copolymer, acrylonitonyl-butadiene-styrene copolymer, polyphenylene oxide, polyphenylene oxide-polystyrene mixture or copolymer, ethylene -Propylene copolymer, ethylene-propylene-
Examples thereof include a diene copolymer, an ethylene-butene-1 copolymer and a mixture of the above thermoplastic resins.

The silicone oil used in the present invention preferably has a structural unit represented by the following formula.

However, R ¹ and R ² may be the same or different and each is a hydrogen atom, a hydroxyl group, a saturated or unsaturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group or an aryl group. R ¹ and R ² are preferably methyl groups or phenyl groups. Furthermore, the viscosity of silicone oil (25 ℃) is about 600-3
00,000,000 centipoise, preferably 10,000-150,000
It is a centipoise.

The silicone resin used in the present invention is a known one available in various forms and is soluble in the above silicone oil. R ¹ ₃ SiO Preferred silicone resins
_0.5 units are composed of SiO units.

The composition of the present invention comprises a thermoplastic resin of 50 to 98 parts by weight, preferably 60 to 96 parts by weight, a silicone oil of 1 to 30 parts by weight, preferably 2 to 25 parts by weight, a silicone resin of 1 to 20 parts by weight, preferably 2 to Consists of 15 parts by weight.

The hindered amine compounds used in the present invention include, for example, bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate and 4-benzoyloxy-2,2,6,6.
-Tetramethylpiperidine, polycondensate of succinic acid and N- (2-hydroxyethylene) -2,2,6,6 tetramethyl-4-hydroxypiperidine, 1,2,3,4-tetra (2,2 ,
6,6-Tetramethyl-4-piperidyl) -butanetetracarboxylate, 1,4-di- (2,2,6,6-tetramethyl-4-piperidyl) -2,3-butanedione, tris-
(2,2,6,6-Tetramethyl-4-piperidyl) trimellitate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4- Piperidyl-n-octoate, bis- (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tris- (2,2,6,
6-Tetramethyl-4-piperidyl) -nitrile acetate, 4-hydroxy-2,2,6,6-tetramethylpiperidyl, 4-hydroxy-1,2,2,6,6-pentamethylpiperidine, 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]], N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane However, the polycondensation product of the present invention is not limited thereto.

The hindered amine compound is added in an amount of 0.01 to 5.0 parts by weight, preferably 0.03 to 1.0 part by weight, based on 100 parts by weight of the composition. If it is less than 0.01 parts by weight, the effects of improving flame retardancy and weather resistance cannot be obtained, while if it is 5 parts by weight or more, not only is it uneconomical, but problems such as bleeding and deterioration of appearance are caused.

It is preferable to add a Group IIA metal organic salt to the composition of the present invention because the flame retardancy is further improved. The Group IIA metal organic salt is preferably a carboxylate. Examples are magnesium stearate, calcium stearate, barium stearate, zinc stearate, strontium stearate. Other carboxylic acid salts include isostearic acid,
Salts such as oleic acid, palmitic acid, myristic acid, laxeric acid, untesilenic acid, 2-ethylhexanoic acid, bivalic acid and hexanoic acid are included.

The amount of Group IIA metal organic salt added is 1 per 100 parts by weight of the composition.
-30 parts by weight, preferably 2-20 parts by weight.

When a phenolic antioxidant is used in combination with the composition of the present invention, flame retardancy and weather resistance are further improved, which is preferable.

Examples of phenolic antioxidants include 2,6-di-
Tertiary butyl-P-cresol, stearyl- (3.5-
Di-methyl-4-hydroxypentyl) thioglycolate, stearyl-β- (4-hydroxy-3,5-di-tertiary butylphenyl) propionate, distearyl-
3,5-di-tertiary butyl-4-hydroxybenzylphosphonate, 2,4,6-tris (3 ', 5'-di-tertiary butyl-4'-hydroxybenzylthio) -1,3,5 -Triazine, distearyl (4-hydroxy-3-methyl-5-
Tert-Butyl) benzyl malonate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol) 4,4'-
Methylenebis (2,6-di-tert-butylphenol), 2,
2'-methylenebis [6- (1-methylcyclohexyl) p-cresol], bis [3,5-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4'-butylidene bis (6 -Third
Butyl-n-cresol), 2,2'-ethylidene bis (4,6-di-tert-butylphenol), 2,2'-ethylidene bis (4-tert-butyl-6-tert-butylphenol), 1,1 , 3-Tris (2-methyl-4-hydroxy-
5-tert-butylphenol) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris ( 2,6-dimethyl-3-hydroxy-
4-tert-butyl) benzyl isocyanurate, 1,3,5-
Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 2,6-diphenyl-
4-octadecyloxyphenol, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-tris (3,5-
Di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,35-tris [(3,5-di-tert-butyl-4-
Hydroxyphenyl) propionyloxyethyl] isocyanurate, 2-octylthio-4,6-di (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, 4,4'-thiobis ( 6-tert-butyl-m-cresol) and the like.

The amount of these phenolic antioxidants added is 10
0.01 to 5.0 parts by weight, preferably 0.03 to 0 parts by weight
It is 1.0 weight.

It is preferable to use an ultraviolet absorber together with the composition of the present invention because the weather resistance is further improved. Examples of ultraviolet absorbers include
2-Hydroxy-4-methoxybenzophenone, 2-Hydroxy-4-octoxybenzophenone, 2-Hydroxy-4-stearyloxybenzophenone, 2-Hydroxy-4-dotesiloxybenzophenone, 2-Hydroxy-4-methoxy-benzophenone-5 -Sulfonic acid, 2
-Hydroxy-4-methoxy-4-methylbenzophenone, 2-hydroxy-4-benzoyloxybenzophenone, 5-chloro-2-hydroxy-benzophenone, 2,
4-dihydroxybenzophenone, 2,2-dihydroxy-
4-methoxybenzophenone, 2,2-dihydroxy-4,4
-Dimethoxybenzophenone, 2,2-dihydroxy-4
Hydroxybenzophenones such as -n-octoxybenzophenone, phenyl salicylate, P-butylphenyl salicylate, P-octylphenyl salicylate, resorcinol monopenzoate, 2,4-di-t-butyl-phenyl-3, Benzoates such as 5-di-t-butyl-4'-hydroxybenzoate and 4-octylphenyl-3,5-di-t-butyl-4-hydroxybenzoate.
2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-
Butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-amylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-isoamylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5' -Di-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-
5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tbutylphenyl) -5-chlorobenzotriazole, 2-
(2'-hydroxy-3 ', 5'-dimethylphenyl)-
Examples thereof include benzotriazoles such as 5-chlorobenzotriazole and 2- (2'-hydroxy-3 ', 5'-dichlorophenyl) benzotriazole.

The amount of these ultraviolet absorbers added is 0.01 to 5.0 parts by weight, preferably 0.03 to 1.0 part by weight, based on 100 parts by weight of the composition.

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

It is preferable to use a phosphorus acid antioxidant in combination with the composition of the present invention because the weather resistance is further improved. Examples of phosphorus-based antioxidants include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl-
Diphenylphosphite, tris (2,4-di-tert-butylphenyl) phosphite, triphenylphosphite, tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearylbentaerythritol diphosphite, tetra (tridecyl)
-1,1,3-Tris (2-methyl-5-tert-butyl-4-
Hydroxyphenyl) butane di phosphite, tetra (O ₁₂ ~ ₁₅ mixed alkyl) -4,4'-isopropylidene diphenyl phosphite, tetra (tridecyl) -4,
4'-butylidene bis (3-methyl-6-tert-butylphenol) diphosphite, tris (3,5-di-tert-butyl-4-hydroxyphenyl) phosphite, tris (mono / di-mixed nonylphenyl) phosphite, hydrogenated- 4,4'-isopropylidene diphenol polyphosphite, bis (octylphenyl) .bis [4,4'-butylidene bis (3-methyl-6-tert-butylphenol)]. 1,6-hexadiol diphosphite, Phenyl 4,4'-isopropylidenediphenyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4) -Methylphenyl) pentaerythritol diphosphite, tris [4,4'-isopropylidene bis (2-tert-butylpheno] )] Phosphite, phenyl diisodecyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, tris (1,3-di-stearoyloxyisopropyl) phosphite, 4,4′-isopropylidene bis (2
-Tert-butylphenol) -di (nonylphenyl) phosphite, 9,10-di-haloid-9-oxa-10-phosphaphenanthrene-10-oxide, tetrakis (2,4-di-tert-butylphenyl) Examples include −4,4′-biphenylenediphosphonite.

The addition amount of these phosphorus antioxidants is 0.001 to 5 parts by weight, preferably 0.01 to 1.0 parts by weight, based on 100 parts by weight of the composition.

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 dialkylthiodipropionate such as dilauryl-, dimyristyl-, and distearyl- and butyl-, octyl-,
Lauryl-, stearyl-, and other alkylthiopropionic acid polyhydric alcohols (e.g., glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) esters (e.g. pentaerythritol tetrakis (dodecylthiopropionate)) Can be mentioned.

The amount of these sulfur antioxidants added is 0.001 to 5.0 parts by weight, preferably 0.01 to 1.0 parts by weight, per 100 parts by weight of the composition.

In addition, if necessary, the composition of the present invention may be a nucleating agent, a metallic soap, a plasticizer, an epoxy compound, a pigment, a filler, a foaming agent, an antistatic agent, a lubricant, or another flame retardant agent that does not adversely affect weather resistance. , Processing aids and the like can be included.

<Examples> Next, the present invention will be specifically described with reference to Examples. However, the present invention is not limited to these examples.

Examples 1 to 5 Melt flow rate 8.5 g / 10 min., Ethylene content 8 wt%
2: 1 mixture of methyl silicone oil and methyl silicone resin (Toshiba Silicone SFR-100) magnesium stearate and various additives were blended with the above propylene-ethylene block copolymer at a ratio shown in Table 1, It was melt extruded at 230 ° C. using a shaft extruder and pelletized by a pelletizer. And the thickness by injection molding method
A 4 mm flat plate was created. Length 127 mm, width 12.7 from this plate
mm flammability test pieces and weather resistance test pieces were cut out. The flammability test was evaluated according to the method defined in UL standard UL94. In the combustion test of 5 test pieces per test, the maximum time of the first ignition combustion time and the second ignition combustion time was defined as the maximum ignition combustion time. For the weather resistance test, an accelerated weather resistance test is carried out with a sunshine weatherometer (black panel temperature: 83 ° C, spray / dry cycle: 18 minutes / 102 minutes), and the time until abnormal appearance such as cracks on the surface of the test piece occurs It was time.

 The results are summarized in Table 1.

However, the contents of various additives shown in Table 1 are as follows.

A-1; bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate, A-2; poly [[6- (1,1,3,3-tetramethylbutyl)
Imino-1,3,5-triazine-2,4-diyl] (2,2,6,6
-Tetramethyl-4-piperidine) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] B-1; tetrakis [methylene-3- (3 ', 5'-di -T
-Butyl-4-hydroxyphenyl) propionate]
Methane B-2; 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, C-1; 2- (2'-hydroxy-3'-t-butyl-
5'-methylphenyl) -5-chlorobenzotriazole C-2; 2,4-cy-t-butyl-phenyl-3 ', 5'-di-t-butyl-4'-hydroxybenzoate, D-1 Bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, D-2; dimyristyl thiodipropionate Comparative Example-1 The procedure of Example-1 was repeated, except that various additives were not added. The results are shown in Table 1.

<Effect of the Invention> According to the present invention, flame retardancy and weather resistance are improved by blending a thermoplastic resin with a silicone oil, a silicone resin and a hindered amine compound.

Claims (1)

(57) [Claims] 1. A thermoplastic resin of 50 to 98 parts by weight b) Silicone oil of 1 to 30 parts by weight c) Silicone resin of 1 to 20 parts by weight, and a hindered amine compound of 0.01 to 5.0 parts by weight per 100 parts by weight of the composition. A flame-retardant resin composition characterized by being mixed in parts by weight.