JPS605614B2 - flame retardant composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a terpolymer of acrylonitrile, butadiene and styrene; an organic flame retardant additive containing chlorine and/or bromine; and an iron compound selected from the specified group. The present invention relates to a novel scaly plastic composition.

These new compositions exhibit high flame retardancy, improved mechanical properties and low toxicity, and can be manufactured economically. Various applications of plastic compositions require that the inherent flammability of the composition be substantially reduced.

It is known to use organic compounds of chlorine or bromine as additives for this purpose. Although these additives are effective, the amount required to impart the desired degree of flame retardance is dependent on other important properties of the composition, such as mechanical strength (strength properties such as tensile and impact strength). ), modulus, strain temperature, etc., are so large as to cause considerable damage. It is also known to use antimony trioxide as an aggressive additive to reduce the amount of halogen compounds required in these compositions. However, antimony trioxide is expensive, and the substance's recent history, limited availability, and price instability make it difficult to rely on it as the only substance for this purpose. was dangerous. In the case of acrylonitrile-butadiene-styrene terpolymers (A mottled resins), antimony trioxide or mechanical properties such as impact strength are undesirably side-effected. However, when the terpolymer is combined with 'a' an organic flame retardant additive containing chlorine and/or bromine and 'b' an iron compound selected from a specific group, the conventional It has now been found that the present invention provides highly useful flame retardant plastic compositions which have considerable advantages over known compositions.

In this case, iron compounds have almost no elutriation effect on the above polymers in the absence of halogen compounds, but exhibit a strong strengthening effect on the halogen compounds in these polymers. Additionally, this combination has wide latitude in the selection of compounds for particular properties and end uses based on the effectiveness of the wide variety of halogen and iron additives useful in this invention. If the polymer is a common ABS resin, these combinations create highly flame-retardant, high-impact plastic compositions without the use of expensive antimony, chromium or tin additives, or toxic fluorine compounds. give.

By oxygen index and burn rate criteria, this composition exhibits much more effective flame retardancy than similar compositions containing a wide variety of other metal compounds. The compositions of the present invention can also be made into sponges by well known methods, such as by incorporating blowing agents, to obtain low density flame retardant materials useful for applications such as insulating materials, floating materials, etc. .

The use of the iron compounds of the invention offers new advantages, inter alia in terms of cost, raw material availability and low toxicity.

Furthermore, although the substitution of antimony trioxide would present disadvantages to the mechanical properties of the composition, the high degree of scaly activity obtained with low concentrations of iron compounds minimizes the disadvantages to these properties. or, in the case of iron oxides, a considerable improvement in these properties. The plastic terpolymer consisting of acrylonitrile, butadiene and styrene used in the present invention (Amo resin) is a plastic terpolymer consisting of acrylonitrile, butadiene and styrene, which is composed of styrene and acrylonitrile on a rubber-like polymer such as polybutadiene, styrene-butadiene rubber, or acrylonitrile-butadiene rubber. or a mixture of such a graft polymer and a styrene-acrylonitrile copolymer, suitable ABS resins are those described in U.S. Pat. No. 3,686,362, shelf 1, lines 50 to 3. Column 2
Line 1 and Column 3 No. 15 of Specification No. 3809725
It is disclosed to the guardian of number 3.

The organohalogen-containing flame retardant additives used in the present invention are well known and belong to a recognized group of flame retardant additives for polymers.

These include aliphatic, aromatic, cycloaliphatic, or mixed chlorine and/or bromine containing compounds whose halogen content typically ranges from 1 to 8% by weight. hydroxyl group,
Other groups other than halogens, such as anhydride groups, ether groups, carboxyl groups, ester groups and phosphate groups, also do not inhibit the flame retardation activity of the iron compound when they are combined with the compound and are An object may exist as long as it does not lose its advantageous properties. These halogen compounds should be substantially non-volatile and stable at polymer processing temperatures and non-reactive with the polymer and any other auxiliary components such as rubber curing agents. . on the other hand,
Even poorly stabilized halogen compounds can be stabilized by additives such as organotin stabilizers commercially available for polyvinyl chloride, which makes these halogen compounds stable even at polymer processing temperatures. The halogen compound may optionally be a polymer such as polyvinyl halide (polyvinyl chloride), neoprene or chlorinated polyethylene. Mixtures of halogen compounds may also be used.The invention Examples of non-polymeric chlorine and bromine compounds useful in carrying out the process include:

"Chiorowa x", "Unichlor" and "Celechlor"
Chlorinated paraffins are commercially available under various trade names such as "Tetrapromethane, Hexabromobutane-2, Tribrome neobentyl alcohol, Dibrome neobentyl glycol, Zip. Mubutenediol and its diacetates, methylbentachlorstearate and tris(mono- and dihaloalkyl)
Phosphates; hexar, octa- and decabromo biphenyls, decabromodiphenyl oxide, hexabromobenzene, tribromophenol, tetraprom salicylanilide, tetra(pentabromophenoxy)silane, dibromopropylchlorobenzoate, Halogenated aromatic compounds such as dibromopropyl maleate, titrachloro and tetrabromoophthalic anhydrides, tetrachlor- and tetrabromo-bisphenol A and their bis-hydroxypropyl derivatives; hexabromocyclododecane, venta Bromochlorocyclohexane, bis(cyclohexenyl)ethylene hexabromide, hexachlorocyclobentadiene (HCCPD) and its derivatives (specifically, Diels-Alda addition compounds with positive or cyclic dienes or olefins) ,
These include, for example, chlorendic acid with furan, benzoquinone, vinylnorbornene, cyclooctadiene, bentadiene, etc., chlorendic acid anhydride, chlorendic acid dimethyl ester, chlorendic acid diallyl ester "Cloran", perchlorobentacyclodecane and HCCPD adducts).

The amount of halogen compound used will vary depending on the particular compound and will be determined by the desired degree of flame retardancy and tolerance limits for other properties.

Generally, at least 1 part of halogen compound per 100 parts by weight of polymer is required to provide effective flame retardancy.
Typically, the amount of halogen compound used is
It ranges from 1 to 30 parts by weight per 0 parts by weight. Preferably it is 1 to 110 parts by weight, most preferably 5 to 4 parts by weight. However, apart from property requirements, the reinforcing effect of iron compounds used in combination with halogen compounds can be maintained even at much higher quantitative levels of halogen compounds, so even higher amounts of halogen compounds can be used. can. Iron compounds that can be used include ferric oxide, triferric tetroxide, ferrous and ferric sulfate, ferrous and ferric ammonium sulfate, iron carbonate, ferrous sulfide, in anhydrous and hydrated form. , ferrous, ferric, ferrous ammonium and ferric ammonium salts of carboxylic acids such as acetic acid, stearic acid, oxalic acid and citric acid, and iron salts of resin acids.

Both basic and neutral salts can be used as well as anhydrous and hydrated forms of the salts. Mixtures of these iron compounds can also be used. If appropriate, mixtures with other metal compounds such as antimony trioxide may also be used. These iron compounds have a high level of flame retardancy, as measured by oxygen index standards, when obtaining higher levels of flame retardancy than those obtained with other metal compounds, and when obtaining these benefits at low concentrations. The combination has a remarkable effect. The amount of iron compound used, as with halogen compounds, depends on the desired balance between flame retardancy and other properties, as well as the particular iron compound chosen.

Generally, at least about 0.0% per part by weight of polymer 10.
A portion of the iron compound is necessary to obtain significant flame retardancy over that provided by the halogen compounds. However, there is little advantage in using more than 5 anchors of iron compound per 10 anchors of polymer. 1 to 25 parts of iron compound per 10 parts of polymer are preferred, and 1 to 1 part of iron compound is most preferred. The plastic compositions of the present invention are readily obtained by conventional plastic compounding methods and converted into finished articles by methods well known to the art.

It is also clear that any smaller amount of polymer than that desired in the final composition can be combined in any suitable manner with the iron and halogen compounds, and the resulting concentrated raw material (i.e. masterbatch) then Combined with additional polymers in a conventional manner. Such operations are effective in improving the dispersion of the flame retardant component in the final composition.
With respect to the concentrated raw materials, the polymer may be used in whole or in part as appropriate to the processability and properties of the final composition.
Of course, it is also possible to substitute other polymers that do not interfere with the action of the flame retardant system. The concentrate may further contain processing aids and/or other ingredients that meet the same requirements as described above. The flame retardant composition of the present invention and its method of preparation will become clearer from the following examples.

These examples are set forth as illustrative of the invention and are not intended to be, nor should they be construed as, limiting. In the examples, A
Compounding of BS test samples was carried out in a conventional manner using a mill for rubber plastics. Platy test samples were compression molded, cut to size and finished to pass the test method. The ABS polymer used was a 50/5 weight percent blend of resin and grafted terpolymer containing 22% acrylonitrile, 23% butadiene and 55% styrene. The graft terpolymer is 70/3 weight percent of styrene and acrylonitrile.
The mixture was a grafted 90/10 putadiene/styrene emulsion copolymer rubber. The resinous component was a conventional emulsion polymerized 70/3 weight percent styrene noacrylonitrile copolymer. The following named halogen compounds are among the compounds used in the examples below.

"Cloran" 1, 2, 3, 4, 9, 9 - Hexachlororu 1, 4, umbrella,
5, 6, 7, 8, Soichi octahydro 1,4-methanonaphthalene-6,7-dicarboxylic acid anhydride.

2 packs of Polyvinyl Chloride Marvinol (Marvino 1) Medium molecular weight general purpose resin, intrinsic viscosity (ASTMD-124)
3-66) = 0.93 Specific gravity = 1.40 and oil adsorption degree (
cc/(ASTM D-281) = 0.9.

The sample was tested as follows. 1 Oxygen index: A
STM method D-2863 "Flammability of plastics using the oxygen method".

The oxygen index is the lowest concentration of oxygen in a slowly rising nitrogen and oxygen mixture, expressed in volume percent, that just supports combustion of the burning material under equilibrium conditions of candle-like combustion.

A higher oxygen index indicates lower relative flammability. Because this method provides a continuous numerical scale to give relative flammability ratings, it is well suited to account for differences in flame retardation imparted by additives and additive combinations in polymers: ABS resins. ing.

"Δ01" in all examples represents the increase in oxygen index over that of the base polymer provided by the additive or combination of additives. 2. Horizontal burn rate and vertical burn test performance were determined at the distances indicated with respect to the number of test specimens and without predetermined conditions as appropriate, substantially in accordance with the following procedure:

a Horizontal burning rate: ASTM D-635-63 "Flammability Test of Hard Plastics".

Three or more samples of the specified dimensions were used per test. 10. Compositions that did not burn up to the 16 arc (4 inch) mark were designated as "SE" (self-extinguishing) in the examples.
Compositions that did not burn to the 2.54 arc (1 inch) mark were designated as "NB" (non-flammable).

b Vertical combustion test performance: UL Chapter 94, material at 94V-
Vertical combustion test for classification as 0, 94-V-1 or 94-V-2. of the thickness indicated for each composition, 12
．． Five 5 inch x 1 inch plate specimens were tested under "conditioned" conditions. Example
1 This example demonstrates the strong elutriation effect given by the combination of an iron compound and a halogen compound in a suitable polymer, shown in (i) to (t). This is explained in contrast to the weak effect of the compound alone.

*M&T Chemicals Co., Ltd.
Organotin mercaff, a stabilizer for polypinyl chloride, commercially available from Micals, Inc.

Chido "Thermolite 31"
)” stabilized. In Example 1 and the following examples, ferric sulfate is used as a hydrate, while ferrous sulfate is used in anhydrous form unless otherwise specified. Example 2 This example demonstrates the effectiveness of a wide range of additional iron compounds used in combination with halogen compounds in ABS resins, and also presents test data for antimony trioxide to illustrate the high effectiveness of iron compounds. has been done.

Halogen compound: Polychlorinated pinyl
olumbian Oarbon○o. Mapico Yello-1050 (Mapico Yello-1050) commercially available from )
wl050) The same polymer but without iron compounds, the oxygen index was 27.7 (
Δ01=19.2) was obtained.

This proves that iron compounds greatly reduce the amount of halogen compounds required. Example 3 This example further illustrates the effectiveness of iron compounds used in combination with cycloaliphatic chlorine compounds in ABS.

Halogen compound: "chlorane", 30 h Example 4
The examples demonstrate the high effectiveness of the iron compound/halogen compound combination in flame retardant polymer compositions, also by horizontal combustion tests.

In the data shown below, the size of the material used is 1
2.7 arc x 1.27 x 0.318 skin (5 inches x 1/
2 inches x 1'8 inches). Also, "NB" indicates no combustion, ie, the flame did not reach the starting line 1 inch from the end for measuring the burn rate. Polymer: ABS Halogen compound: Polypinyl chloride This explains the great effect of iron compounds as

In the data shown below, "NB" has the same meaning as in Example 4, "SE" indicates no combustion up to the mark of 10.16 kites (4 isochi), and stannic oxide water as an additive. The first data about Japanese products is ``Journal''.
of Fire and Framability (J.
Fire & Flammability), Volume 3, Page 136 (1972). Polymer: A
BS resin halogen compound: polypynyl chloride, 2opph halogen compound: /mi-chlorobentacyclodecane, 25pp
Some samples were either SB or NB.

Example 6 This example demonstrates that the presence of ferric oxide significantly reduces the amount of halogen compound required to impart a given flame rating to a polymer composition.

Polymer: ABS x Stabilized with Thermolite 31 Example 7 This example uses ferric oxide in place of antimony trioxide in obtaining a polymer composition with high flame retardancy and improved impact strength. This explains the advantages of time.

In the following data, notched impact test (Notch
The sample used in the edlxodImpactTest was a compression molded sample with a thickness of 0.32 arc (1'). Polymer: ABS x stabilized with Thermolite 31.

Example 8 This example illustrates the advantageous effect of ferric oxide over antimony trioxide on the impact strength of ABS compositions containing halogen compounds obtained when processing conditions become increasingly severe. It is something.

In this example, the sample used had a thickness of 0.32 skin (1
It was a compression molded sample of ``A'', ``B'', and ``C''.
and ABS composition represented by "D" following conditions: "A"
-171.1℃ (3400F) for 10 minutes, "B" -17
1.30 minutes at 100 (3400F), "C" - 204.
4oo (4000F) for 30 minutes, and "D"-204.
The mixture was kneaded at 4 qo (4000F) for 60 minutes before molding. Izod impact strength with nose (ft.lbs
/inch-zotch width) Example 9 This example further illustrates that the reinforcing effect of ferric oxide used in combination with a suitable halogen compound in a polymer is obtained over a wide range of concentrations of the halogen compound. It is.

Polymer: ABS Halogen compound: polyvinyl chloride Stabilized with Thermorite 31.

Compositions (g) and (h)' have a thickness of 0.16 arc (1/16
The vertical combustion test gave the following results:

Claims (1)

[Claims] 1 A plastic terpolymer consisting of acrylonitrile, butadiene and styrene, and an effective flame retardant amount (
a) substantially at the processing temperature of the polymer having a halogen content of 35 to 80% by weight and optionally containing oxygen substituents in the form of hydroxyl, anhydride, ether, carboxyl, ester or phosphate groups; non-volatile,
and (b) an organic additive selected from the group consisting of stable chlorinated and brominated aliphatic, aromatic and cycloaliphatic hydrocarbyl compounds, and mixtures thereof; diiron, triiron tetroxide and mixtures thereof, basic and neutral ferrous and ferric sulfates,
Ferrous and ferric ammonium sulfates, iron carbonate, ferrous sulfide, ferrous salts, ferric salts, ferrous ammonium salts of aliphatic carboxylic acids optionally containing a hydroxyl group as a substituent, A flame retardant composition characterized in that it consists of an iron compound selected from the group consisting of ferric ammonium salts, iron salts of the resin group and mixtures of said iron compounds.