JPH0798891B2 - High light resistance flame retardant resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a highly light-resistant flame-retardant resin composition having a high degree of light resistance, flame retardancy, and impact resistance.

[Problems to be Solved by Conventional Techniques and Inventions]

Styrenic resins, especially ABS resins, have excellent impact resistance, heat resistance, mechanical properties, electrical properties, molding processability, and many other features such as a beautiful appearance, so they are widely used in household appliances and office equipment. It is used in large quantities for household items. At the same time, since styrene resin is prone to burning, UL
Various regulations regarding flame retardancy such as standards have been strengthened,
Has many usage restrictions.

Flame retardation of styrene-based resin is mainly carried out by adding a compound containing halogen, phosphorus or the like, or a flame retardant such as antimony trioxide, and the purpose is to add these flame retardants. Although flame retardancy is obtained, it often adversely affects other physical properties.

Further, with the spread of office equipment such as computers and facsimiles in recent years, in addition to flame resistance and impact resistance, excellent light resistance is also strongly demanded in order to reduce discoloration due to light from fluorescent lamps.

Conventionally, it has been known that a flame retardant in which a terminal of a halogenated bisphenol A type epoxy resin is sealed with tribromophenol is blended with a styrene resin in order to improve light resistance.
No. 63-72749.

However, when a flame retardant in which the end of halogenated bisphenol A type epoxy resin is sealed with tribromophenol is used for general ABS resin, the light resistance tends to be improved, but it is required in the market especially in the OA field. It is not improved to the level of light resistance, and the impact resistance, especially the falling weight impact strength is low and not practical. This is presumably because the flame retardant has poor compatibility or dispersibility with general ABS resin. In order to improve the above-mentioned falling weight impact strength, it is necessary to increase the rubber content, so that thermal stability, fluidity, rigidity,
Furthermore, flame retardancy is impaired, and simply blending a flame retardant in which the end of halogenated bisphenol A type epoxy resin is blocked with tribromophenol into ABS resin has an excellent quality balance and high light resistance. In reality, it is extremely difficult to obtain a flame ABS resin composition.

[Means for Solving the Problems]

In view of such a situation, the present inventors have conducted extensive studies to obtain a resin composition having high light resistance and flame retardancy and excellent impact resistance, and as a result, have a specific structure for a resin composition having a specific composition. The present invention has been accomplished by adding a halogen-containing compound having the formula (3), and further adding a chlorinated polyethylene compound, a benzotriazole type ultraviolet absorber, a sterically hindered amine type light stabilizer and titanium oxide.

That is, the present invention is a resin composition obtained by polymerizing a monovinyl aromatic monomer and an unsaturated nitrile monomer in the presence of a rubber-like substance, wherein the rubber-like substance content is 8 to 24% by weight. There is a copolymer content of monovinyl aromatic compound units and unsaturated nitrile compound units is 76 to 92 wt%, and the proportion of unsaturated nitrile compound units in the copolymer is 25 to 35 wt% And 100 parts by weight of the resin composition having a graft ratio to the rubber-like substance of 40% to 70%, (X is bromine or chlorine, a, b, c and d are natural numbers of 1 to 5, n is the number of repetitions and the average value of n is in the range of 0.5 to 2.2) alone or in combination of two or more. 12 to
26 parts by weight, chlorinated polyethylene compound 1 to 10 parts by weight, benzotriazole-based UV absorber 0.1 to 2.0 parts by weight, sterically hindered amine light-resistant stabilizer 0.05 to 2.0 parts by weight and titanium oxide 0.5 to 10 parts by weight. Is a flame-retardant resin composition having high light resistance. Hereinafter, the present invention will be described in detail.

The monovinyl aromatic monomer used in the present invention means α-substituted styrene such as styrene and α-methylstyrene: nuclear-substituted styrene such as vinyltoluene, m-chlorostyrene, p-chlorostyrene and p-methylstyrene. Etc., and one or more of these are used. Most preferred is styrene.

Examples of the unsaturated nitrile monomer used in the present invention include acrylonitrile and methacrylonitrile. Acrylonitrile is preferably used.

The proportion of the unsaturated nitrile compound unit in the copolymer composed of the monovinyl aromatic compound unit and the unsaturated nitrile compound unit in the resin composition used in the present invention needs to be 25 to 35% by weight, preferably Is 27 to 33% by weight.

If the amount of the unsaturated nitrile compound exceeds 35% by weight, the impact strength decreases, and if it is less than 25% by weight, the impact strength similarly decreases.

Examples of the rubber-like substance used in the present invention include natural rubber, polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, polychloroprene, acrylic rubber, ethylene-propylene rubber, ethylene-propylene-diene monomer rubber, styrene- Examples thereof include vinyl acetate copolymers. Among them, polybutadiene and butadiene-styrene copolymer are preferable.

The content of the copolymer composed of the monovinyl aromatic compound unit and the unsaturated nitrile compound unit in the resin composition is 76 to 92% by weight, while the content of the rubber-like substance is 8 to 24% by weight.
It is necessary to be, and preferably 12 to 20% by weight. When the content of the rubber-like substance is less than 8% by weight, the impact strength is lowered, and when it exceeds 24% by weight, the flame retardancy, light resistance, fluidity,
Properties such as rigidity and thermal stability deteriorate. Further, the graft ratio of the resin composition onto the rubber-like substance is required to be 40 to 70%, preferably 50 to 60%. Graft rate
If it is less than 40%, the impact strength will decrease, and if it exceeds 70%, the impact strength will decrease.

The resin composition used in the present invention can be produced by ordinary emulsion polymerization, bulk polymerization, bulk one-suspension polymerization, or the like. If necessary, a separately produced copolymer of a monovinyl aromatic monomer containing no rubbery substance and an unsaturated nitrile monomer may be mixed.

The content of the rubber-like substance and the proportion of the unsaturated nitrile compound unit in the copolymer can be measured by a commonly used method, for example, an infrared spectrophotometer.

The graft ratio to the rubber-like substance in the present invention is obtained from the following formula by dissolving a certain weight of resin in acetone, separating the acetone insoluble matter using a centrifuge, drying and weighing.

The halogen-based flame retardant used in the present invention is generally represented by the following formula.

In the above formula, X is bromine or chlorine, and a, b, c and d are 1 to 5
, N is the repeating number, and the average value of n of the halogen-containing compound is a range of 0.5 to 2.2, preferably 0.8 to 1.5. If the average value of the number of repetitions n is less than 0.5, the heat resistance of the flame-retardant resin composition is poor, and if the average value of n is more than 2.2, the light resistance and impact resistance are deteriorated.

The halogen-based flame retardant is used alone or in combination of 2 or more 12 to 26 parts by weight with respect to 100 parts by weight of the resin composition. Compounding amount is 12
If it is less than part by weight, the required flame retardancy cannot be obtained, and if it exceeds 26 parts by weight, not only is it economically disadvantageous, but also the impact resistance is significantly lowered.

The halogen-based flame retardant used in the present invention is obtained by reacting a halogenated bisphenol A type epoxy resin with halogenated phenols such as tribromophenol, dibromocresol, trichlorophenol and dichlorocresol by heating in the presence of a basic catalyst. can get.

The number of repetitions n of the halogen-based flame retardant used in the present invention was obtained by calculation after obtaining the molecular weight by gel permeation chromatography.

In the present invention, 1 to 10 parts by weight, preferably 3 to 7 parts by weight of a chlorinated polyethylene compound is added to 12 to 26 parts by weight of a specific halogen-based flame retardant per 100 parts by weight of the above resin composition.

Surprisingly, improvement in impact resistance was found, which is considered to be an effect that the chlorinated polyethylene compound greatly improves the dispersibility of the specific halogen-based flame retardant in the resin composition. If the amount of the chlorinated polyethylene compound added is less than 1 part by weight, the impact resistance improving effect is small, and if it is more than 10 parts by weight, the thermal stability during injection molding becomes poor and the rigidity of the molded product decreases. Is not preferable.

In the present invention, in addition to 12 to 26 parts by weight of a specific halogen-based flame retardant with respect to 100 parts by weight of the resin composition, 0.1 to 2.0 parts by weight of a benzotriazole-based ultraviolet absorber, a sterically hindered amine light-resistant stabilizer 0.05 to 2.0 parts by weight and titanium oxide 0.5-10
Mix parts by weight.

With respect to 100 parts by weight of the resin composition, when the benzotriazole-based ultraviolet absorber is less than 0.1 parts by weight, the light resistance is not significantly improved, and when it is more than 2.0 parts by weight, the heat resistance is lowered and the addition is expensive. Because it is a drug, it is not economical. When the amount of the sterically hindered amine-based light stabilizer is less than 0.05 parts by weight, the light resistance improving effect is small, and when it is more than 2.0 parts by weight, the heat resistance is lowered and the additive is expensive, which is not economical.

If the amount of titanium oxide is less than 0.5 parts by weight, the effect of improving the light resistance is small, and if it is more than 10 parts by weight, the impact resistance decreases, which is not preferable.

As the benzotriazole-based ultraviolet absorber, 2- (5
-Methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole,
2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-
Methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2
-(3,5-di-t-amyl-2-hydroxyphenyl)
Benzotriazole, 2- (2'-hydroxy-5'-
t-octylphenyl) benzotriazole, methyl-
3- [3-t-butyl-5- (2H-benzotriazol-2-yne) -4-hydroxyphenyl) propionate-condensation product with polyethylene glycol, hydroxyphenylbenzotriazole derivative and the like.

As the sterically hindered amine-based light resistance stabilizer, dimethyl succinate 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [{6- (1 , 1,3,3-Tetramethylbutyl) amino-1,
3,5-Triazine-2,4-diyne} {2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,
2,6,6-Tetramethyl-4-piperidyl) imino}],
N, N'-Bis (3-aminopropyl) ethylenediamine ・ 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4piperidyl) amino] -6-chloro-1 , 3,5-
Triazine condensate, bis (2,2,6,6-tetramethyl-4
-Piperidyl) sebacate, succinic acid-bis (2,2,6,6
-Tetramethyl-4-piperidinyl) ester, 2-
(3,5-di-t-butyl-4-hydroxybenzyl) -2
Bis (1,2,2,6,6-pen (tamethyl-4-piperidyl) -n-butylmalonate, and the like.

In the present invention, the above-mentioned resin composition and halogen-based flame retardant, chlorinated polyethylene compound, benzotriazole-based UV absorber, sterically hindered amine-based light stabilizer and titanium oxide have a high degree of light resistance and flame retardancy. It is possible to obtain a highly light-resistant flame-retardant resin composition having the following characteristics and excellent impact resistance, and the present invention is not achieved even if any one is missing.

The method for producing a highly light-resistant flame-retardant resin composition of the present invention comprises a resin composition containing a specific halogen-based flame retardant and a chlorinated polyethylene compound as a light-resistant prescription, a benzotriazole-based UV absorber, a sterically hindered amine-based light-resistant stabilizer, and The method of blending titanium oxide is not particularly limited, and there are methods such as a tumbler mixer, a super mixer, a Banbury mixer, a kneader, a roll, a single screw extruder, and a twin screw extruder. Moreover, you may mix | blend at the time of manufacture of a resin composition.

If necessary, various additives may be added to the composition of the present invention within a range not impairing the object of the present invention. As various additives, a plasticizer, a lubricant, a flame retardant aid, a stabilizer, a filler, a reinforcing agent, a coloring agent and the like can be added.

〔Example〕

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples.
This does not limit the scope of the invention. The composition of the present invention was evaluated by the methods described below. However, pellets were used as the melt flow rate, and injection molded test pieces were used for the other tests.

・ Izod impact strength: ASTM D 256 test piece thickness 6.4 mm, with notch ・ Tensile strength, elongation: ASTM D 638 ・ Melt flow rate: ISO R 1133 temperature 200 ° C, load 5 kg ・ Heat deformation temperature: ASTM D 648 test Piece thickness: 6.4 mm, no annealing Bending stress: 18.6 kg / cm ²・ Light resistance: The discoloration degree of the test piece after 300 hours with a Canon arc weatherometer was measured with a color difference meter and expressed as the difference from the unexposed sample. .

・ Flame resistance: UL-94 test piece thickness 1/8 inch, 1/12 inch VO rank is judged.

・ Drop weight impact strength: 150 mm square, thickness 3 mm, drop missile (R = 3/4 inch) on a flat plate molded product with one pin gate.
Change the missile, the load on the missile, and the missile drop distance (distance from the missile tip to the surface of the molded product).
Calculate the fracture energy at which the part cracks.

・ Thermal stability test: IS80-A manufactured by Toshiba Machine Co., Ltd., cylinder temperature 230 ° C, mold temperature 60 ° C, molding time 20 minutes,
3rd shot color chip (90mm × 50mm × 2.5mm t)
Comparatively observe the burnt state of.

・ Rubber amount: A resin composition was compressed into a thin film at a temperature of 200 ° C., and the film was measured with an infrared spectrophotometer (Hitachi: EPI, G-3) at 1601 cm ^-1 , 967 cm
Measure the absorption ratio of the absorption band of ^-1 and measure the amount of rubber with the calibration curve prepared in advance.

- ratio of AN units in the copolymer: a resin composition into a thin film by compression at 200 ° C., the film infrared spectrophotometer (manufactured by Hitachi, Ltd.: EPI, G-3) at 2250 cm ^-1, 1601 cm The absorbance in the absorption band of ^-1 is measured, and the amount of AN in the copolymer is measured by a calibration curve prepared in advance.

-Measurement of the number of repetitions n of the halogen-based flame retardant: The number of repetitions n was calculated in terms of molecular weight in terms of styrene compound polymer by measuring the molecular weight by gel permeation chromatography.

・ Measuring instrument manufacturer and model TOYO SODA, HLC-802A ・ Measurement conditions Solvent: Tetrahydrofuran Temperature: 38 ℃ Concentration: 20mg / 20ml Solvent (A) Polymerization of resin composition Polybutadiene latex with an average particle size of 3000Å, styrene, acrylonitrile, usually used Using the chain transfer agent, the emulsifier, and the ion-exchanged water, emulsion polymerization was performed by a conventional method to obtain ABS resins A-1 to A-7 shown in Table 1.

(B) Halogen-containing compound Table 2 shows the halogen-containing compounds used in Examples and Comparative Examples.

[Additive (I)] As the chlorinated polyethylene, Daisolac G235 manufactured by Osaka Soda Co. was used.

[Additive (II)]

As the benzotriazole-based ultraviolet absorber, the following third
The one shown in the table was used.

[Additive (III)] As the sterically hindered amine light stabilizer, those shown in Table 4 below were used.

[Additive (IV)] As titanium oxide, ICI (UK) trade name RTC-30
It was used. As the zinc oxide, the special issue of Sakai Kagaku was used.

Example 1 The following mixing ratios were mixed in a drum blender and then kneaded at a temperature of 220 ° C. by a twin-screw extruder with a 35 m / mφ bend to form pellets.

Cylinder temperature 220 ℃, mold temperature 60
Injection molding was performed at ℃, and various physical properties were measured. The results are shown in Table 5.

Examples 2 to 4 and Comparative Examples 1 to 16 Resin compositions, halogen-based flame retardants and additives (I) to (I
The same procedure as in Example 1 was carried out except that the mixing ratio of V) was changed as shown in Table 5. The results are shown in Table 5.

[Effects of the Invention] The highly light-resistant flame-retardant resin composition of the present invention is a flame-retardant resin composition having excellent impact resistance while having a high degree of light resistance, and is an industrial material, particularly office equipment, electric equipment. It is extremely useful industrially as a housing material.

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Claims (1)

[Claims] 1. A resin composition obtained by polymerizing a monovinyl aromatic monomer and an unsaturated nitrile monomer in the presence of a rubber-like substance, wherein the content of the rubber-like substance is 8 to 24% by weight. The copolymer content of the monovinyl aromatic compound unit and the unsaturated nitrile compound unit is 76 to 92% by weight, and the proportion of the unsaturated nitrile compound unit in the copolymer is 25 to 35% by weight. 100 parts by weight of the resin composition having a graft ratio to the rubber-like substance of 40 to 70%, (X is bromine or chlorine, a, b, c and d are natural numbers of 1 to 5, n is the number of repetitions and the average value of n is in the range of 0.5 to 2.2) alone or in combination of two or more. 12 to
26 parts by weight, chlorinated polyethylene compound 1 to 10 parts by weight, benzotriazole-based ultraviolet absorber 0.1 to 2.0 parts by weight, sterically hindered amine light-resistant stabilizer 0.05 to 2.0 parts by weight, and titanium oxide 0.5 to 10 parts by weight. A highly light-resistant flame-retardant resin composition comprising: