JPH066673B2 - 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 the thermoplastic resin is flammable, flame retardancy is regulated depending on the application.

[Conventional technology]

To make a thermoplastic resin flame-retardant, a polychlorinated organic compound,
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, the halogen-based flame retardant is unstable at high temperatures and easily decomposes, so that the thermoplastic resin containing it 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-58-790).
No. 46) and a method of adding a dialkyl tin malate polymer (Japanese Patent Publication No. 47-20090).

[Problems to be solved by the invention]

However, since the above thermoplastic resin has a particularly high processing temperature (200 ° C. or higher), thermal stabilization at high temperature is not sufficient by any method, and development of an excellent stabilizer for preventing this thermal deterioration has been demanded. There is. [Means for Solving the Problems] As a result of various studies, the present inventors have added a halogen-based flame retardant-containing thermoplastic resin by adding an organic tin thiodipropionate or / and an organic tin dithiodipropionate. We have found that the resin can be heat-stabilized and filed an application. However, we have found that the flame-retardant resin can be heat-stabilized to a higher degree by using a combination of the above-mentioned organotin compound and dialkyltin maleate compound, and arrived at the present invention. .

That is, the present invention is a resin 100 selected from polyolefin resin, styrene resin, polyester resin, nylon resin, polyacetal resin and polycarbonate resin.
(A) dialkyltin thiodipropionate, monoalkyltin thiodipropionate, dialkyltin dithiodiene when heat-stabilizing a flame-retardant resin comprising 1 part by weight and 1 to 50 parts by weight of a halogen-based flame retardant. 1 of an alkyltinthio or dithiodipropionate consisting of a propionate and a monoalkyltin dithiodipropionate
One or more of 0.01 to 5 parts by weight and (b) 0.01 to 5 parts by weight of a dialkyltin maleate or / and a dialkyltin maleate salt are added in combination, which is a stabilized composition. It is a flammable thermoplastic resin composition.

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, for example, a compound having a repeating unit of the general formula [2] as a repeating unit, and examples of dialkyl tin dithiodipropionate include a compound having a repeating unit of the general formula [3] as a monoalkyl tin dithio compound. 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.

Examples of the dialkyltin maleate salt added in the present invention include compounds of the general formula [5], and examples of dialkyltin maleate salts include the compound of the general formula [6].
And the compound of [7] can be mentioned respectively.

In the formula, R is an alkyl group such as a methyl group, a butyl group, an octyl group and a lauryl group, and R ¹ is a methyl group,
Ethyl group, butyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, lauryl group, cetyl group, stearyl group, behenyl group, oleyl group, myristyl group, benzyl group, cyclohexyl group, methoxybutyl group , A methylbenzyl group, a hydrocarbon group such as a higher alkyl group derived from a higher alcohol synthesized by the oxo method, and n represents an integer of 1 to 10, respectively.

In the present invention, the amount of alkyltin thio or dithiodipropionate added is 0.01 per 100 parts by weight of the thermoplastic resin.
Up to 5 parts by weight, and the addition amount of dialkyltin maleate or dialkyltin maleate is 10% by weight of the thermoplastic resin.
It is 0.01 to 5 parts by weight with respect to 0 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, methylstyrene mainly containing styrene, 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 Mention may be made of polyacetal 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, chloroendo acid, hexachloroethane, hexachlorocyclohexane, pentachlorobenzene, etc. Is, for example, tetrabromoethane, tetrabromobutane, bromide of an aliphatic hydrocarbon such as tribromopropane, tribromotrichlorocyclohexane, tetrabromodichlorocyclohexane, bentabromocyclohexane, 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.

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, borohydride). Acid salts, aluminum hydroxide, etc.), smoke suppressants (smokeless agents), pigments, fillers,
A lubricant or the like can be added.

[Action]

A thermoplastic resin containing a halogen-based flame retardant can be heat-stabilized by adding one or more of alkyltin thio or dithiodipropionate, but according to the present invention, a dialkyltin maleate or / and a dialkyltin are further added. Addition of the tin maleic acid ester salt improved the thermal stability of the resin and made the processing at high temperature extremely easy. Such effects cannot be achieved with metal salts of other carboxylic acids.

〔Example〕

The present invention will be described below with reference to examples, but parts in the examples are 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 0.5 parts 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 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 230 ° 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), 20 parts of hexabromocyclododecane, 1 part of titanium oxide and 1.0 part 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 225 ° 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, 25 parts of perchloropentacyclodecane, 10 parts of antimony trioxide and 2.0 parts of the stabilizer shown in Table 3 below were added and mixed with a kneading roll at 180 ° C for 3 minutes to form a sheet having a thickness of 0.5 mm. Created. This sheet is sandwiched between aluminum plates, 22
Thermal stability tests were performed in a gear oven maintained at 5 ° 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, 15 parts of a tetrabromobisphenol A carbonate oligomer (Fireguard 7000, manufactured by Teijin Chemicals Ltd.), 3 parts of antimony trioxide and 0.3 part of a stabilizer shown in Table 4 below were added and mixed with a Henschel mixer. The sheet was extruded with a 20 mm extruder (extrusion conditions are as follows) to form a sheet having a thickness of 1 mm. This sheet was sandwiched between aluminum plates, and a thermal stability test was performed in a gear oven maintained at 240 ° 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 thermal stability tests of Examples 1 to 4, in the present invention, a halogen-based flame retardant-containing thermoplastic resin is used as an alkyltinthio or dithiodipropionate salt.
When a dialkyltin maleate or / and a dialkyltin maleic acid ester salt is added together, one kind or two or more kinds,
The resin can be heat-stabilized to a higher degree, and processing at higher temperatures becomes easier. 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 flame retardant. Upon stabilization, (a) an alkyltinthio or dithiodipropion consisting of a dialkyltin thiodipropionate, a monoalkyltin thiodipropionate, a dialkyltin dithiodipropionate and a monoalkyltin dithiodipropionate. 1 of acid salt
One or more of 0.01 to 5 parts by weight and (b) 0.01 to 5 parts by weight of a dialkyltin maleate or / and a dialkyltin maleate salt are added in combination, which is a stabilized composition. Flammable thermoplastic resin composition.