JPH064763B2 - Stabilized flame-retardant thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermally stabilized thermoplastic resin composition containing a halogen-based flame retardant.

Thermoplastic resins such as polyolefin resins, styrene resins, polyester resins, nylon resins, polyacetal resins and polycarbonate resins have excellent physical properties and are therefore used in various applications such as electrical appliances, upholstery and building materials. ing. However, since thermoplastic resins are flammable, flame retardance is regulated depending on the application.

[Conventional technology]

To make thermoplastic resins flame-retardant, polychlorinated organic compounds,
Add flame retardants such as polybrominated organic compounds, antimony trioxide, and phosphorus compounds. Among them, halogen-based flame retardants such as polychlorinated organic compounds and polybrominated organic compounds are effective.
Often used.

However, halogen-based flame retardants are unstable at high temperatures and easily decompose, so the thermoplastic resin containing them is colored during processing.

Therefore, in order to prevent coloring due to these flame retardants, a method of adding a metal salt of dehydroacetic acid (JP-A-58-79046).
A method of adding a dialkyl tin malate polymer (Japanese Patent Publication No. 47-20090) is known.

[Problems to be solved by the invention]

However, since the above-mentioned thermoplastic resin has a particularly high processing temperature (200 ° C or higher), heat stabilization at high temperature is not sufficient by any of the methods, and development of an excellent stabilizer for preventing this heat deterioration is desired. There is.

[Means for solving problems]

As a result of various studies, the present inventors have found that a halogen-based flame retardant-containing thermoplastic resin can be thermally stabilized even at high temperature processing by adding an organotin thiodipropionate and / or an organotin dithiodipropionate. The present invention has been completed and the present invention has been achieved.

That is, the present invention provides a resin 100 selected from a polyolefin resin, a styrene resin, a polyester resin, a nylon resin, a polyacetal resin, and a polycarbonate resin.
When heat-stabilizing a flame-retardant resin consisting of 1 part by weight and 1 to 50 parts by weight of a halogen-based flame retardant, a dialkyltin thiodipropionate, a monoalkyltin thiodipropionate,
One or more dialkyltin dithiodipropionate and monoalkyltin dithiodipropionate are added in an amount of 0.01 to
The stabilized flame-retardant thermoplastic resin composition is characterized by adding 5 parts by weight.

Examples of the dialkyltin thiodipropionate to be added to the flame-retardant resin for thermal stabilization in the present invention include a compound having a repeating unit of the structure of the general formula [1] as a monoalkyltin thiodipropionate. Examples of the compound include a compound having a repeating unit of the general formula [2] as a repeating unit, and examples of dialkyltin dithiodipropionate include a compound having a repeating unit of the general formula [3] as a monoalkyltin dithiodione. Examples of the dipropionate include compounds having the network structure of the general formula [4] as a repeating unit.

In the formula, R represents an alkyl group such as a methyl group, a butyl group, an octyl group and a lauryl group.

In the present invention, the addition amount of alkyltin thio or dithiodipropionate is 0.01 per 100 parts by weight of the thermoplastic resin.
~ 5 parts by weight. If it is used below the lower limit of this amount, the thermal stability is not improved, and if it is above the upper limit, it is uneconomical.

Examples of the thermoplastic resin to be flame-retarded in the present invention include polyolefin resins such as polyethylene and polypropylene, for example, polystyrene, styrene-based methylstyrene, divinylbenzene, butadiene, copolymers with acrylonitrile, acrylonitrile butadiene styrene. Styrenic resins such as terpolymers, acrylonitrile / butadiene / methylstyrene terpolymers, butadiene / styrene or acrylonitrile copolymers, and mixtures of styrene / acrylonitrile copolymers, such as polyethylene terephthalate, poly Polyester resin such as butylene terephthalate, nylon resin such as nylon 6, nylon 66, nylon 11, nylon 12 such as acetal homopolymer, acetal copolymer, etc. Mention may be made of acetal resin and polycarbonate resin.

In the present invention, a halogen-based flame retardant of a polychlorinated organic compound and a polybrominated organic compound is used to make the thermoplastic resin flame-retardant. As the polychlorinated organic compound, for example, polychloroparaffin, chlorinated polyethylene, perchloropentacyclodecane, tetrachlorophthalic anhydride, chlorendo acid, hexachloroethane, hexachlorocyclohexane, pentachlorobenzene, etc. Are, for example, bromides of aliphatic hydrocarbons such as tetrabromoethane, tetrabromobutane, tribromopropane, tribromotrichlorocyclohexane, tetrabromodichlorocyclohexane, pentabromocyclohexane, tetrabromocyclooctane,
Hexabromocyclododecane, bromide of alicyclic hydrocarbon such as bis (dibromocyclohexyl) -1,2-dibromoethane, hexabromobenzene, decabromodiphenyl, decabromodiphenyl ether, hexabromodiphenyl ether, pentabromodiphenyl ether,
Pentabromotoluene, pentabromoethylbenzene,
Pentabromophenol, tribromophenol, 1,
2-dibromopropyltribromophenyl ether, tetrabromobisphenol A, tetrabromobisphenol S, tetrabromophthalic anhydride, 1,2-bis (pentabromophenoxy) ethane, bis (tribromophenoxy) ethane, polydibromophenylene oxide, etc. Examples thereof include aromatic bromides and carbonate oligomers of tetrabromobisphenol A.

Addition amount of halogen-based flame retardant is 1 to 50 parts by weight to 100 parts by weight of thermoplastic resin, and addition amount of one or more of alkyltinthio or dithiodipropionate is 0.01.
~ 5 parts by weight.

In the composition of the present invention, if necessary, an antioxidant, an ultraviolet absorber, boric acid, a boric acid ester, an epoxy compound, a metallic soap, a diketone compound, a flame retardant other than a halogen-based compound (for example, a phosphorus compound, antimony trioxide, boron). Acid salt, aluminum hydroxide, etc.), smoke remover (smokeless agent), pigment, filler,
A lubricant or the like can be added.

[Work]

According to the present invention, a thermoplastic resin containing a halogen-based flame retardant can be highly heat-stabilized, and the resin can be easily processed at high temperatures. Such effects cannot be achieved with metal salts of other carboxylic acids.

〔Example〕

Next, the present invention will be described with reference to examples, but parts in the examples represent parts by weight.

Example 1 100 parts of acrylonitrile butadiene styrene resin (Cycolac Ex211 manufactured by Ube Cycon), 20 parts of tetrabromobisphenol A, 5 parts of antimony trioxide and 0.3 part of the stabilizer shown in Table 1 below were added, and the temperature was changed to 150 ° C. The sheets were mixed with a kneading roll for 4 minutes to form a sheet having a thickness of 0.5 mm. This sheet was sandwiched between aluminum plates and a thermal stability test was conducted in a gear oven maintained at 220 ° C.

The numbers in the table represent the following evaluations.

1: White 2: Light yellow 3: Yellow 4: Light brown 5: Brown 6: Black brown The results are shown in Table 1.

Example 2 100 parts of a styrene resin (Stylon 666, manufactured by Asahi Kasei), 25 parts of hexabromocyclododecane, 1 part of titanium oxide and 0.7 parts of a stabilizer shown in Table 2 below were added, and a kneading roll at 135 ° C. for 3 minutes And a sheet with a thickness of 0.5 mm was prepared.
This sheet was sandwiched between aluminum plates and a thermal stability test was conducted in a gear oven maintained at 220 ° C.

The numbers in the table represent the following evaluations.

1: White 2: Light gray 3: Gray 4: Black gray 5: Black The results are shown in Table 2.

Example 3 Polypropylene resin (E-100G, manufactured by Idemitsu Petrochemical Co., Ltd.) 1
00 parts, perchloropentacyclodecane 20 parts, antimony trioxide 10 parts and dioctyltin thiodipropionate 0.
1, 0.5, 1.0, 2.0, 3.0 and 5.0 parts were added and mixed with a kneading roll at 180 ° C. for 3 minutes to prepare a sheet having a thickness of 0.5 mm. This sheet was sandwiched between aluminum plates and a thermal stability test was conducted in a gear oven maintained at 220 ° C.

The numbers in the table represent 6 grades from white to light gray.

The results are shown in Table 3.

Example 4 Polyester resin (Tough pellet N100, Mitsubishi Rayon Co., Ltd.), nylon resin (S1040, Unitika Co., Ltd.), polyacetal resin (Duracon M90, Polyplastics Co.) or polycarbonate resin (Panlite L1250, Teijin Chemicals Co., Ltd.) 100 parts, carbonate oligomer of tetrabromobisphenol A (Fireguard 7000, Teijin Chemicals Ltd.) 15. %, Antimony trioxide 3 parts, dibutyltin thiodipropionate 0.5 part were added, mixed with a Henschel mixer, and extruded with a 20 mm extruder (extrusion conditions are as follows),
A sheet having a thickness of 1 mm was prepared. This sheet was sandwiched between aluminum plates and a thermal stability test was conducted in a gear oven maintained at 230 ° C.

The numbers in the table represent 6 grades from white to light brown.

The results are shown in Table 4.

[Effects of the Invention] As is clear from the results of the heat-stable production test of Examples 1 to 4, in the present invention, the halogen-based flame retardant-containing thermoplastic resin is used as the alkyltinthio or dithiodipropionate 1
By adding one or two or more species, the resin can be highly heat-stabilized and the processing at high temperature becomes easy. Such an effect is first achieved by the configuration of the present invention.

Claims (1)

[Claims] 1. A flame-retardant resin comprising 100 parts by weight of a resin selected from a polyolefin resin, a styrene resin, a polyester resin, a nylon resin, a polyacetal resin and a polycarbonate resin and 1 to 50 parts by weight of a halogen-based flame retardant. Upon stabilization, the alkyltin thio or dithiodipropionate consisting of dialkyltin thiodipropionate, monoalkyltin thiodipropionate, dialkyltin dithiodipropionate and monoalkyltin dithiodipropionate A stabilized flame-retardant thermoplastic resin composition, characterized in that 0.01 to 5 parts by weight of one or more are added.