JPH0680131B2 - Stabilized flame-retardant styrene resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a heat-stabilized flame-retardant styrene resin composition.

Since styrene resins have excellent physical properties, they are used in various applications such as electric appliances, upholstery and building materials. However, since styrene-based resins are flammable, flame-retardant regulations are imposed for some applications.

[Conventional technology]

To make the styrene resin flame-retardant, flame retardants such as polychlorinated organic compounds, polybrominated organic compounds, antimony trioxide, and phosphorus compounds are added. Of these, halogen-based flame retardants are particularly effective and are often used. However, halogen-based flame retardants are unstable at high temperatures and are easily decomposed, so styrene-based resins containing them are colored during processing.

Therefore, in order to prevent coloring by these flame retardants, organic tin compounds (Japanese Patent Publication No. 47-22090), organic tin compounds and antioxidants (Japanese Patent Publication No. 46-16481, Japanese Patent Publication No. 47-9744),
Hydrotalcite (JP-A-60-86143) and the like are added.

[Problems to be solved by the invention]

However, since the above styrenic resin has a particularly high processing temperature (200 ° C or higher), the addition of an organic tin compound (and an antioxidant) has an insufficient effect of suppressing coloration during processing, and the addition of hydrotalcite When added, plate-out is significant, and thermal stability and initial colorability are unsatisfactory. There is a demand for the development of excellent stabilizers that prevent these thermal deterioration and plate-out.

[Means for solving problems]

As a result of various studies, the present inventors have found that by adding a perchlorate ion type hydrotalcite compound, a styrene resin containing a halogen-based flame retardant can be thermally stabilized even at high temperature processing, and plate out can be improved. The present invention has been found under the heading.

That is, according to the present invention, when heat-stabilizing a flame-retardant resin comprising 100 parts by weight of a styrene resin and 1 to 50 parts by weight of a halogen-based flame retardant, 0.01 to 5 parts by weight of a perchlorate ion type hydrotalcite compound is used. It is a stabilized flame-retardant styrene resin composition characterized by being added in parts.

Further, the present invention provides a method for thermally stabilizing the above flame retardant resin,
(A) Add a perchlorate ion type hydrotalcite compound to 0.
01-5 parts by weight and (b) 0.01-5 parts by weight of one or more of dialkyltin maleate, dialkyltin maleate, dialkyltin thiodipropionate or dialkyltin dithiodipropionate. It is a stabilized flame-retardant styrene-based resin composition characterized by being added together with.

In the present invention, the perchlorate ion-type hydrotalcite compound added to thermally stabilize the flame-retardant resin has the general formula MgxAly (OH) _{2x + 3y-2z} (A ^2- ) _z · aH ₂ O (formula medium a ^2-in ▲ CO ^2- ₃ ▼ ^2-valent anion such as, x, y and z is Is a positive number that satisfies Is obtained by contacting hydrotalcites represented by the formula (1) with perchloric acid in the presence of water and exchanging 20 to 80% of divalent anions such as carbonate ion with perchlorate ion. .

Examples of the styrene resin used in the present invention include polystyrene, methylstyrene mainly containing styrene, divinylbenzene, a copolymer with butadiene acrylonitrile, an acrylonitrile / butadiene / styrene terpolymer, and acrylonitrile / butadiene / methylstyrene. Examples thereof include a terpolymer, a mixture of butadiene and styrene or acrylonitrile, and a mixture of styrene and acrylonitrile.

In the present invention, a halogen-based flame retardant of a polychlorinated organic compound and a polybrominated organic compound is used for flame retarding the styrene resin. Examples of polychlorinated organic compounds include perchloropentacyclodecane, tetrachlorophthalic anhydride, chloroendo acid, hexachloroethane, hexachlorohexane, and pantachlorobenzene, and examples of polybrominated organic compounds include tetrabromoethane. , Bromides of aliphatic hydrocarbons such as tetrabromobutane and tribromopropane, tribromotrichlorocyclohexane, tetrabromodichlorocyclohexane, pentabromocyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (dibromocyclohexyl) -1,2 Alicyclic hydrocarbon bromide such as dibromoethane, hexabromobenzene, decabromodiphenyl, decabromodiphenyl ether, hexabromodiphenyl ether, pentabromo Phenyl ether, pentabromotoluene, pentabromoethylbenzene, pentabromophenol, tribromophenol, 1,2-dibromopropyltribromophenyl ether, tetrabromobisphenol A, tetrabromobisphenol S, tetrabromophthalic anhydride, 1,2-bis Aromatic bromides such as (pentabromophenoxy) ethane, bis (tribromophenoxy) ethane, polydibromophenylene oxide, and carbonate oligomers of tetrabromobisphenol A can be used.

A perchlorate ion-type hydrotalcite compound can be added to the flame retardant resin of the present invention to achieve sufficient thermal stabilization. However, when higher thermal stabilization is required, dialkyltin maleate, dialkyltin are used. The purpose can be achieved by further adding one or more of a maleic acid ester salt, a dialkyltin thiodipropionate or a dialkyltin dithiodipropionate.

Examples of the dialkyltin maleate include compounds of the general formula [1], and examples of dialkyltin maleate salts include compounds of the general formulas [2] and [3].

In the formula, R is an alkyl group such as a methyl group, a butyl group, an octyl group or a lauryl group, and R ¹ is a methyl group,
Ethyl group, butyl group, peptyl 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 , Hydrocarbon groups such as higher alkyl groups derived from higher alcohols synthesized by the oxo method, where n is 1
Each represents an integer of ~ 10.

As the dialkyltin thiodipropionate, for example, a compound having the structure of the general formula [4] as a repeating unit, and as the dialkyltin dithiodipropionate, for example, the structure of the general formula [5] as a repeating unit Each of the compounds may be mentioned.

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 perchlorate ion type hydrotalcite is 0.01 to 5 relative to 100 parts by weight of styrene resin.
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.
When a higher degree of thermal stability is required, dialkyltin maleate, dialkyltin maleate, dialkyltin thiodipropionate or dialkyltin dithiodipropionate may be used in an amount of 0.01 or more. ˜5 parts by weight may be added. 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.

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.

[Action]

According to the present invention, a styrene-based resin containing a halogen-based flame retardant can be highly heat-stabilized by adding a perchlorate ion-type hydrotalcite compound obtained by contacting hydrotalcites with perchloric acid. ， It becomes easy to process flame retardant resin at high temperature. When hydrotalcites that are not treated with perchloric acid are used, plate-out occurs during processing and the effect of the present invention cannot be achieved. By adding the dialkyltin compound of the present invention to the perchlorate ion type hydrotalcite compound, the thermal stability of the flame retardant resin can be further improved.

〔Example〕

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

Preparation of chlorate ion type hydrotalcite Preparation 1 Disperse 0.5 mol of commercially available hydrotalcite (Alkamizer 1, manufactured by Kyowa Chemical Industry Co., Ltd.) in 3 liters of water under high speed stirring, and add 0.8 mol of 70% aqueous solution of perchloric acid. The appropriate amount was gradually added and mixed well. When the generation of carbon dioxide gas was completed, the stirring was stopped and a wet powder mixture was obtained. This was dried at 50 ° C. under reduced pressure to obtain sample A.

Preparation 2 0.5 mol of hydrotalcite (Alkamizer 1) was reacted with 0.6 mol of perchloric acid, and Sample B was prepared in the same manner as in Preparation 1.
Got

Preparation 3 Synthetic hydrotalcite (DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.)
Sample C was obtained in the same manner as in Preparation 1 by reacting 0.4 mol with 0.5 mol of perchloric acid.

Preparation 4 Synthetic hydrotalcite (DHT-4A) 0.5 mol perchloric acid
Sample D was obtained in the same manner as in Preparation 1, except that 0.2 mol was allowed to act.

Example 1 100 parts of acrylonitrile-butadiene-styrene resin (Cycolac Ex211, manufactured by Ube Cycon), 10 parts of tetrabromobisphenol A, 5 parts of antimony trioxide and the perchlorate ion type hydrotalcite compound shown in Table 1 below (sample 0.3 parts of A to D) were added and mixed by a kneading roll at 150 ° C. for 4 minutes to prepare a sheet having a thickness of 0.5 mm. At this time, the plate-out property on the roll was observed. This sheet was sandwiched between aluminum plates and a thermal stability test was conducted in a gear oven maintained at 230 ° C. Further, the same tests and observations were carried out in the case where 0.3 part of commercially available hydrotalcite (Alkamizer 1) was added and the case where it was not added.

The numbers and symbols in the table represent the following evaluations.

1: White 2: Light yellow 3: Yellow 4: Light brown 5: Brown 6: Black brown ○: No plate-out △: Slight plate-out ×: Significant plate-out results are shown in Table 1.

Example 2 100 parts of acrylonitrile butadiene styrene resin (Cycolac Ex211), 15 parts of a carbonate oligomer of tetrabromobisphenol A (Fireguard 7000, manufactured by Teijin Chemicals Ltd.), 7 parts of antimony trioxide, perchlorate ion type hydrotal. 0.2 part of the site compound (Sample C) and 0.3 part of the organotin compound shown in Table 2 below were added and mixed by a kneading roll at 150 ° C. 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 carried out in a gear bun kept at 230 ° C.

The numbers in the table have the same meaning as the evaluation in Example 1.

The results are shown in Table 2.

Example 3 100 parts of a styrene resin (Stylon 666, manufactured by Asahi Kasei), 10 parts of hexabromocyclododecane, 1 part of titanium oxide and 0.5 parts of a perchlorate ion type hydrotalcite compound (Samples A to D) shown in Table 1 below. Parts were added and mixed with a kneading roll at 130 ° C for 3 minutes to prepare a 0.5 mm thick sheet. At this time, the plate-out property on the roll was observed. This sheet was tested for thermal stability in a gear oven maintained at 220 ° C.

The numbers in the table represent the following evaluations, and the symbols have the same meanings as in Example 1.

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

Example 4 Styrene resin (Styron 666) 100 parts, hexabromocyclododecane 10 parts, antimony trioxide 5 parts, perchlorate ion type hydrotalcite compound (Sample B) 0.5 part and the organotin compound 0.5 of the following Table 4 Parts were added and mixed with a kneading roll at 130 ° C for 3 minutes to prepare a sheet with a thickness of 0.5 mm.
This sheet was subjected to a thermal stability test in a gear oven maintained at 230 ° C.

The numbers in the table represent the following evaluations.

1: White color 2: Light yellow 3: Yellow color 4: Light brown 5: Light black brown 6: Black 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 above, in the present invention, perchlorate ion type hydrotalcite or organic compounds thereof with a halogen-based flame retardant-containing styrene resin are used. The addition of a tin compound made the resin highly heat-stabilized and facilitated processing at high temperatures. Further, as is clear from Examples 1 and 3, by adding perchlorate ion type hydrotalcite, it became possible to prevent the defect caused by the addition of commercially available hydrotalcite, that is, plate out. Such an effect is first achieved by the configuration of the present invention.

Claims (2)

[Claims] 1. When heat-stabilizing a flame-retardant resin comprising 100 parts by weight of a styrene resin and 1 to 50 parts by weight of a halogen-based flame retardant, 0.01 to 5 parts by weight of a perchlorate ion type hydrotalcite compound is used. A stabilized flame-retardant styrene-based resin composition, which is added. 2. When heat-stabilizing a flame-retardant resin comprising 100 parts by weight of a styrene-based resin and 1 to 50 parts by weight of a halogen-based flame-retardant, (a) a perchlorate ion-type hydrotalcite compound is used.
01-5 parts by weight and (b) 0.01-5 parts by weight of one or more of dialkyltin maleate, dialkyltin maleate, dialkyltin thiodipropionate or dialkyltin dithiodipropionate. A stabilized flame-retardant styrene-based resin composition, characterized by being added together with.