JPH0794579B2 - Flame-retardant propylene resin composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION The present invention relates to a flame-retardant propylene-based resin composition having excellent weather resistance.

Today, propylene-based resins have electrical, mechanical,
Since it is excellent in formability and inexpensive, it is widely used as a home electric appliance, an automobile article, a household article, a building material or an auxiliary material thereof.

On the other hand, recently, various flame retardants have been obliged to prevent personal injury due to fire.

To make the propylene resin flame-retardant, it is general to use a halogen-based flame retardant and a flame retardant auxiliary together. In particular, among halogen-based flame retardants, bromine-based flame retardants are widely used because of their effectiveness.

However, the propylene-based resin composition flame-retarded by the combined use of the bromine-based flame retardant and flame retardant aid, weather resistance is not improved even if a light stabilizer is added to impart weather resistance,
The range of use of these compositions is greatly restricted.

[Outline of Invention]

SUMMARY OF THE INVENTION The present inventors have conducted extensive studies to improve such defects, and as a result, by using a brominated flame retardant having a specific structure, a flame retardant aid, and an ultraviolet absorber in combination, flame retardancy is improved. The present invention has been completed by finding a propylene-based resin composition having well-balanced weather resistance.

That is, the flame-retardant propylene-based resin composition according to the present invention comprises 100 parts by weight of a propylene-based resin, 0.5 to 80 parts by weight of a brominated flame retardant selected from the following structural formulas [I] and [II], and a flame-retardant auxiliary. 0.2 to 40 parts by weight of agent, and triazole type,
0.01 to 5 parts by weight of at least one UV absorber selected from the group consisting of benzophenone-based, benzoate-based, salicylate-based, and amidine-based, and 0 to 60 parts by weight inorganic filler. It is a thing.

Structural formula [I] Structural formula (II) [Here, each R is a group selected from an alkylene group containing a bromine atom and having 2 or more carbon atoms, a cycloalkylene group, and an arylene group. R'is a group selected from alkyl, cycloalkyl, and aryl groups each containing a bromine atom and having 2 or more carbon atoms. n is an integer of 1-8. Effects According to the present invention, by using a brominated flame retardant having a specific structure together with a flame retardant auxiliary agent and an ultraviolet absorber, it is possible to achieve flame retardancy and weather resistance which were difficult to achieve in the past.

In general, it is well known that bromine-based flame retardants adversely affect weather resistance than chlorine-based ones. Aliphatic flame retardants have weaker binding energy and are unstable. The brominated flame retardant having a specific shape has a small effect on the weather resistance, and when used in combination with a specific ultraviolet absorber, the weather resistance was improved and it was possible to achieve both flame retardancy and weather resistance at the same time. That is surprising.

[Specific Description of the Invention]

[1] Composition component Propylene-based resin The propylene-based resin used in the present invention is a homopolymer of propylene, a random copolymer or block mainly composed of propylene with other α-olefins such as ethylene and butene. Examples thereof include copolymers and mixtures thereof, and among them, melt flow rate (MFR: 230 ° C,
2.16 kg load) 0.1 to 100 g / 10 minutes is preferable.

Flame Retardant The brominated flame retardant used in the present invention has the following structural formula [I].
And a bisimide compound or isocyanurate compound represented by the structural formula [II], both of which contain bromine.

Structural formula [I] Structural formula (II) [Here, each R is a group selected from an alkylene group containing a bromine atom and having 2 or more carbon atoms, a cycloalkylene group, and an arylene group. R'is a group selected from alkyl, cycloalkyl, and aryl groups each containing a bromine atom and having 2 or more carbon atoms. n is an integer of 1-8. The hydrocarbon part of R and R'is usually one having about 2 to 10 carbon atoms, preferably about 3 to 7 carbon atoms. From the viewpoint of flame retardancy, those having a high bromine content are preferable. n is 1 to
It is usually an integer of 8, preferably 2-5.

Some specific examples of such compounds are as follows. Of these, the first three compounds are particularly suitable. The compounds of structural formula [I] and structural formula [II] can be used in combination within each group and between groups, and the present invention is to be understood as such.

Tris (2,3-dibromopropyl) isocyanurate,
Ethylene-bis (5,6-dibromonorbornane-2,3-dicarboximide), 1,2-bis (tetrabromophthalimide) ethane, 1,2-bis (dibromophthalimide) ethane.

The blending amount of these flame retardants is preferably 0.5 to 80 parts by weight per 100 parts by weight of the propylene resin. Particularly, 1 to 70 parts by weight is more preferable. If the blending amount is less than 0.5 parts by weight, sufficient flame retardancy will not be exhibited, while if it exceeds 80 parts by weight, impact resistance will be remarkably reduced and cost will be increased, which is not economical.

Flame Retardant Aid The brominated flame retardant as described above is usually used in combination with a flame retardant aid. This is because it is difficult to further develop the flame retardant effect only with the flame retardant, and it is preferable to use the flame retardant auxiliary together.

Here, the flame retardant aid is one having antimony in the structure.

As the flame retardant aid used in the present invention, antimony compounds such as antimony trioxide, antimony pentoxide and antimony tartrate are preferable. In particular, antimony trioxide is most preferable among them.

Flame retardant aid is 0.2 to 100 parts by weight of propylene resin.
40 parts by weight is preferred.

Ultraviolet Absorber Examples of the ultraviolet absorber used in the present invention include triazole-based, benzophenone-based, benzoate-based, salicylate-based, and amidine-based ultraviolet absorbers, and specific examples thereof include the following ultraviolet absorbers. The ultraviolet absorber suppresses the activation of the propylene resin by light by absorbing ultraviolet rays. Therefore, it is different from the light stabilizer that inactivates the propylene resin activated by light.

(A) 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole (b) 2-hydroxy-4-iso-octoxybenzophenone (c) 2-hydroxy-4-dodecyloxybenzophenone (d) 2-Hydroxy-4-octadecyloxybenzophenone (e) p-octylphenyl salicylate (f) p-t-butylphenyl salicylate (to) 2,4-di-t-butylphenyl-3,5-di-t-
Butyl-4-hydroxybenzoate (thi) n-hexadecyl-3,5-di-t-butyl-4
-Hydroxybenzoate (ri) N- (p-ethoxycarbonylphenyl) -N
-Ethyl-N'-phenylformamidine (nu) 2,2'-dihydroxy-4-methoxybenzophenone (l) 2-hydroxy-4-n-octoxybenzophenone (o) 2,4-di-t-butylphenyl -3,5-di-t-
Butyl-4-hydroxybenzoate (wa) 2- (2'-hydroxy-5'-methylphenyl) benzotriazole (f) 2- (2'-hydroxy-3 ', 5'-di-t-
Amyl-phenyl) benzotriazole (yo) 2- (2'-hydroxy-3'-t-butyl-
5'-methylphenyl) -5-chlorobenzotriazole (ta) 2- (2'-hydroxy-3 ', 5'-di-t-
Butylphenyl) -5-chlorobenzotriazole (le) 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole (so) 2- [2-hydroxy-3,5-bis (α, α-
Dimethylbenzyl) phenyl] -2H-benzotriazole (T) 2- [2'-hydroxy-5'-methyl-3 '
-(3 ", 4", 5 ", 6" -tetrahydrophthalimido-methyl) -phenyl] -benzotriazole The blending amount of the ultraviolet absorber is 0.01 to 5 parts by weight, preferably 0.1 to 100 parts by weight of the propylene resin. ~ 4 parts by weight,
Is.

Some of these ultraviolet absorbers can be expected to further improve the weather resistance by using two or more kinds in combination.

Among the ultraviolet absorbers exemplified above, 2- (2'-hydroxy-3'-t-butyl-5 'is preferred.
-Methylphenyl) -5-chlorobenzotriazole,
2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2-hydroxy-4-n-octoxybenzophenone, 2,4-di-
t-Butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, n-hexadecyl-3,5-di-t
-Butyl-4-hydroxybenzoate and the like.

Inorganic Filler As the inorganic filler used as necessary in the present invention,
Talc, calcium carbonate, zeolite, clay, silica, asbestos, glass fiber, glass beads, glass flakes, mica, calcium oxide, calcium hydroxide,
Aluminum oxide, aluminum hydroxide, zinc oxide, magnesium oxide, magnesium hydroxide, magnesium carbonate, barium sulfate, molybdenum, gypsum, vermiculite, graphite, iron oxide, wollastonite, rock wool,
Examples thereof include potassium titanate whiskers and calcium sulfate whiskers.

The blending amount of these inorganic fillers is preferably 0 to 60 parts by weight per 100 parts by weight of the propylene resin. If it exceeds 60 parts by weight, the impact resistance of the resulting composition is significantly lowered, which is not preferable.

Other components In the composition of the present invention, various rubber components for the purpose of improving impact resistance, antistatic agents such as fatty acid metal salts, fatty acid esters of polyhydric alcohols, titanium oxide, carbon black, etc., if necessary. Various inorganic and organic pigments, phenolic,
Various phosphorus-based and sulfur-based antioxidants, nickel-based hindered amine-based light stabilizers, lubricants, copper damage inhibitors, neutralizing agents, dispersants, hydrotalcite, phosphorus-based, epoxy-based halogen trap agents, etc. Various additives such as the above can be blended.

Further, other thermoplastic resins may be blended within a range that does not adversely affect flame retardancy and weather resistance.

[2] Production of Composition The composition of the present invention is produced by melt-kneading these compounding ingredients by a conventionally known method such as a roll mill, a Banbury mixer, a single-screw extruder and various twin-screw extruders. You can

Further, in order to obtain the composition of the present invention, a high-concentration masterbatch such as a flame retardant, a flame retardant aid, an ultraviolet absorber, etc. may be prepared in advance, and later added at the time of molding.

The use of the composition of the present invention is not particularly limited, but includes wire coatings, injection molded products, films, tapes, sheets, blows,
It can be used as a material for pipes and the like.

Example 1 and Comparative Examples 1 and 2 Mixtures as shown in Table 1 (compounding values are parts by weight) were mixed with a Henschel mixer, melt-extruded with a 40φ single-screw extruder, and pelletized.

Then, a 0.5 mmt sheet was formed by a Placo 35φT die forming machine. The flammability of this sheet was evaluated in accordance with American Motor Vehicle Safety Standard (MVSS) 302. For weather resistance, a sheet of 75 mm × 100 mm was cut out, and this sheet was manufactured by Suga Test Instruments Co., Ltd. Dew Panel Optical Control Weather Ometer (8Hr light / 4Hr dark, 70 ℃ / 50 ℃ cycle)
The photo-deterioration accelerated test was carried out and the generation time of microcracks on the surface of the sheet was visually determined using a 60 × microscope.

The results are shown in Table 1.

Examples 2 to 6 and Comparative Examples 3 and 4 The compounds blended as shown in Table 2 were mixed in a Henschel mixer, melt-extruded in a 40φ single-screw extruder, and pelletized.

Then, using an IS90B injection molding machine manufactured by Toshiba Machine Co., Ltd., a flammability test piece (12.7 mm × 127 mm × 3.2 mmt) defined in UL standard N094.
Also, a sheet of 80 mm × 80 mm × 2 mmt was formed into a weather resistance test piece.

Flammability was determined by the UL94 vertical test method. The weather resistance was determined by the same method as in Example 1.

The results are shown in Table 2.

Example 7 and Comparative Example 5 The ingredients blended as shown in Table 3 were mixed with a Henschel mixer, and then melt-extruded with an Ikegai PCM30φ twin-screw extruder,
Pelletized.

Then, using IS90B injection molding machine manufactured by Toshiba Machine Co., Ltd., UL standard N
A flammability test piece defined in 094 and a 80 mm × 80 mm × 2 mmt sheet were molded to obtain a weather resistance test piece.

Flammability was determined by the UL94 vertical test method. The weather resistance was determined by the same method as in Example 1.

The results are shown in Table 3.

Examples 8 to 11 Evaluations were made in the same manner as in Example 1 except that the type of ultraviolet absorber was changed.

The results are shown in Table 4.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C08L 53/00 LLW // H01B 3/44 G (C08K 13/02 3:00 3:22 5: 00 5:34) (56) Reference JP 61-252256 (JP, A) JP 60-203652 (JP, A) JP 58-13644 (JP, A)

Claims (3)

[Claims] 1. A bromine-based flame retardant selected from the following structural formula [I] and structural formula [II].
To 80 parts by weight, flame retardant aid 0.2 to 40 parts by weight, and at least one UV absorber 0.01 to 5 selected from the group consisting of triazole-based, benzophenone-based, benzoate-based, salicylate-based, and amidine-based A flame-retardant propylene-based resin composition, characterized by comprising 0 to 60 parts by weight of an inorganic filler. Structural formula [I] Structural formula (II) [Here, each R is a group selected from an alkylene group containing a bromine atom and having 2 or more carbon atoms, a cycloalkylene group, and an arylene group. R'is a group selected from alkyl, cycloalkyl, and aryl groups each containing a bromine atom and having 2 or more carbon atoms. n is an integer of 1-8. ] 2. The brominated flame retardant of the above structural formula [I] or structural formula [II] is tris (2,3-dibromopropyl) isocyanurate, ethylene-bis (5,6-dibromonorbornane-2,3). -Dicarboximide) or 1,2-bis (tetrabromophthalimide) ethane, the flame-retardant propylene-based resin composition according to claim 1. 3. The ultraviolet absorber is 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-).
3 ', 5', di-t-butylphenyl) -5-chlorobenzotriazole, 2-hydroxy-4-n-octoxybenzophenone, 2,4-di-t-butylphenyl-3,5-
The flame-retardant propylene resin composition according to claim 1, which is di-t-butyl-4-hydroxybenzoate or n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate. .