CA1062835A - Fire retardant abs-pvc resin compositions - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A resinous composition having fire retardance, impact resistance and easy workability is obtained by blending (1) about 80 to 30 parts by weight of an ABS
resin with (2) about 20 to 70 parts by weight of (i) a vinyl chloride resin compound comprising 100 to 5 parts by weight of a copolymer resin consisting essentially of 0.5 to 40 % by weight of a higher alkyl vinyl ether and 99.5 to 60% by weight of vinyl chloride and (ii) 0 to 95 parts by weight of a polyvinyl chloride resin.

Description

BAC-~GRCU~.D OF THE INVENTION
. . _ . _ .
~ield of the Invention:
~ his invention relates to a novel ABS resin composi-tion improved in fire retardance and workabilityO More particularly, this invention relates to a resinous com-position comprising a blend mixture of an ABS resin and either a copolymer resin consisting essentially of vinyl chloride and a higher alkyl vinyl ether or a vinyl chlo-ride resin compound containing the copolymer.
Description of the Prior Art:
ABS resins (acrylonitrile-butadiene-styrene resins) are of easy-combustibility, and a fire-retarded ABS resin has been keenly neededO
ABS resins have been generally incorporated with fire retardant additives such as halogen-containing compounds and phosphorus-containing compounds and, if desired, together with fire retardant auxiliaries such as antimony trioxide.
Especially, vinyl chloride resins (hereinafter referred to as PVC) have been widely employed as a fire retardant for ABS resins, since PVC is readily blended with ABS resins and does not cause decrease in mechanic-al strength, and bleeding and weathering after a long time of use unlike the case where low-molecular retardant additives such as halogen compounds are employedO
As noted above PVC is an excellent fire retardant for ABS resin, but there remain some processing problems owing to the difference in heat stabilities between PVC
and ABS resin. That is, PVC is inferior in heat stability

- 2 -, 106Z835 to ABS resin. When a blend of PVC and ABS resin is molded at a temperature suitc~ble for processing ABS resin, PVC undergoes thermal decompositionO On the other hand, when the blend is processed at a lower temperature suit-able for PVC, the processing of the blend is extremely difficult because of its very high melt viscosityO
Addition of plasticizers such as dioctyl phthalate and dibutyl phthalate has been proposed so as to elimi-nate these defects, but this method resul-ts in decrease he~ sf~r~ ~m~oerut~ e in hca-~ st~ility of the blend as well as deterioration of fire retardance and great decrease in stiffness in-herent in ABS resin compositions.
SUMMARY 0~ ~HE INVEN~ION
, A series of researches have been made by the present inventors so as to eliminate these defects of PVC to be employed as a fire retardant for A3S resin. ~he inventors have employed a copolymer resin of a higher alkyl-vinyl ether and vinyl chloride or a blend thereof with polyvinyl chloride in place of PVC in ABS resin compositions, and have found that the resulting resinous composition has a satisfactory flow property even at a temperature suitable for processing PVC resin in the same degree as ABS resins and exhibits an excellent hea-t stability.
An object of the invention is thus to provide a high-impact resinous composition which is fire retardant and very excellent in workability or processability.
Other and further objects, features and advantages of the invention will appear more fully from the follow-ing description.

In accordance with the present invention, there is provided a resinous composition having good flow property and fire retardance comprising a blend of (1) about 80 to 30 parts by weight of an ABS resin and (2) about 20 to 70 parts by weight of a vinyl chloride resin compound comprising (i) 100 to 5 parts by weight of a copolymer resin of about OJ5 to 40 % by weight of a higher alkyl vinyl ether and about 99.5 to 60 % by weight of vinyl chloride and (ii) O to 95 parts by weight of a polyvinyl chloride resin.
The resinous composition of the present invention can be advantageously utilized substantially in the same use as conventional ABS resin compositions are employed.
DETAIL~D DESCRIPTION 0~ THE INVENTION
(1) Components of the resinous compositions (a) ABS Resin The ABS resin, one of the main components of the present composition, is basically a ternary polymer comprising polymerized acrylonitrile, or, more broadly a vinyl cyanide, butadiene and styrene or, more broadly, an aromatic vinyl, containing, if desired, a further monomer component such as methyl methacrylate.
Conventional ABS resins are products of polymeri--zation of acrylonitrile and styrene or, more broadly, an aromatic vinyl, in the presence of a butadiene-based rubber polymer such as polybutadiene or a copolymer of butadiene and styrene (SBR). In the present invention, however, it should be understood that the term "ABS resin"

encompasses, in addition to the conventioanl ABS resins J
polymeric mixture of (1) a product of polymerization of either one of an aromatic vinyl such as styrene and a vinyl cyanide such as acrylonitrile in the presence of a butadiene-based rubber polymer such as polybutadiene or a copolymer of butadiene and styrene (SBR), and (2) a copolymer of an aromatic vinyl and a vinyl cyanide.
A part of the styrene can be replaced by another aromatic vinyl compound such as C~-methylstyrene or a vinyl toluene, and the acrylonitrile can be partly replaced by a methacrylic ester such as methyl methacry-late. Moreover, a part or all of acrylonitrile may be replaced by methacrylonitrile.
The ABS resin to be generally employed in the present invention comprises about 10 to 40 parts by weight of a butadiene rubber component, about 80 to 25 parts by weight of an aromatic vinyl compound, and about 35 to 5 parts by weight of acrylonitrile. As to the butadiene rubber component, employed generally are poly-butadiene and/or copolymers consisting of a major part of butadiene and a minor part of a monoolefinic monomer copolymerizable therewith such as styrene, acrylonitrile or vinylidene chloride.
The process for preparation of the ABS resin per se does not comprise any part of the present invention, and the resin is generally produced by either graftpolymeri-zing an aromatic vinyl and acrylonitrile (and/or metha-crylonitrile) onto a butadiene polymer rubber, or graft-polymerizing some parts of the grafting monomer compo-nents onto the rubber and then blending the resulting .. ~
rB

graftpolymer with an aromatic vinyl-acrylonitrile copolymer.
(b) Polyvinyl chloride resin compound The vinyl chloride resin compound to be employed in the present invention is ~A) a copolymer resin consisting essentially of about 0.5 to 40% by weight of a higher alkyl vinyl ether andabout 99.5 to 60% by weight of vinyl chloride (hereinafter referred to as HCA), or ~s) a blend of no less than about 5% by weight of the HCA and not exceeding about 95% by weight of a chloride resin (preferably, vinyl chloride homopolymer resin). Such vinyl chloride resin compound is described in detail in the JapanesePatent Publication No.
22733/1961 of Yuji Hoshi and Mitsuo Onozuka published on November 24, 1961.
When the copolymer resin contains less than about 0.5 % by weight of a higher alkyl vinyl ether, the result-ing resinous composition fails to have sufficient flow property. When the copolymer resin contains more than about 40% by weight of a higher alkyl vinyl ether, it has poor compatibility with the ABS resin and the result-ing resinous composition fails to have good mechanicalproperties. In the same way, the amount of a higher alkyl vinyl ether component contained in the vinyl chloride resin compound is desirable to be not less than 0.5% by weight of the compound.
The higher alkyl vinyl ether of which the alkyl group contains 12 to 18 carbon atoms is generally employ-ed in the present invention. When an alkyl vinyl ether having the alkyl group of less than 12 carbon atoms is used, the resulting resinous composition is inferior in ~B

workability. The alkyl vinyl ether having more than 18 carbon atoms is not suitable since its copolymerizability with vinyl chloride is de~;erioratedO The suitable alkyl vinyl ethers are exemplified by vinyl ethers of lauryl, cetyl, stearyl, myristyl and the likeO These copolymer resins are prepare~ by a conventional suspension or emulsion polymerizationO
In one aspect of the present invention, the vinyl chloride resin compound comprises a blend of a polyvinyl chloride resin in a quantity up to 95 % by weight of the blend. The polyvinyl chloride resin can be any of the resinous polymer of vinyl chloride, and is preferably a homopolymer of vinyl chlorideO
(c) Impact modifiers The resinous composition of the present invention can be further incorporated with an impact modifier which has been employed in conventional vinyl chloride resins.
While ABS resins have excellent impact resistance, it is noted that, in the resinous composition of the present invention, the flow property in processing increases but impact resistance is lowered as the ratio of HCA contained in the vinyl chloride resin compound and the ratio of alkyl vinyl ether contained in the HCA
become larger. The impact resistance of the present resinous composition can be advantageously improved by addition of a small amount of a conventional impact modifier without impairing its good processability.
The amount of the impact modifier to be employed in the present resinous composition varies in accordance with the vinyl chloride resin compound to be e~ployed. ~he impact modifier is generally used in an amount of not more than about 20 parts by weight to 100 parts by weight of the present resinous compositionO
The impact modifiers for vinyl chloride resins are ~xemplified by MBS resin (a terpolymer resin of methyl methacrylate, butadiene and styrene, especially a buta-diene rubber onto which monomer components compri.sing methyl methacrylate and styrene are graft-polymerized), a chlorinated polyethylene, and a ethylene-vinyl acetate copolymer rubber onto which vinyl chloride is graft-polymerized, and the like. The impact modifiers for PV~
on the market can be generally employed.
(d) Other additives As other additives, an antimony compound which is an effective fire retardant auxiliary such as antimony oxide~ antimony trisulfide and triphenyl antimony can be used alone or in combination with other ordinary fire retardant additives.
The fire retardant additives generally employed in the resinous composition are exemplified by chlorinated paraffins, hexabromobenzene, tetrabromoethane, tetra-bromobisphenol A, and the likeO
Suitable amounts of heat stabilizers, lubricants and/or pigments which are generally used in PVC compounds can also be employed upon processing the resinous com-position of the present inventionO
The invention is further explained by way of the following examples, which are illustrative only and are not limitative.
Examples 1 - 10 and comParative examples 1 - ?
A In these examples employed were vinyl chloride-~ rt y l cetyl min~1 ether copolymers containing l~/o and 50/o of cetyl vinyl ether supplied by Kureha Kagaku Kogyo, Japan under the trade name HCA and homopolymers of vinyl chlo-ride having a relatively good flow property supplied by Kureha Kagaku Kogyo under the trade name S9006 (degree of polymerization 600) and S9007 (degree of polymeri%ation 700). ~hey were blended with a commercially available A~S resin comprising 2~/o of acrylonitrile~ 25% of buta-diene and 55% of styrene on the weight basis, to obtain resinous compositions.
One part by weight of organotin maleate stabilizer I ~ tr~e ~qorne ~JL~ (N2000E~supplied by Nitto Chemical Industry CoO, Japan) was added to 100 parts by weight of each of the resin-ous compositions, followed by kneading the mixture on a test roll having surface temperature of 150C to pre-pare sheets. ~he sheets were formed into test pieces by means of press molding~
Fire retardant tests were carried out in accordance with AS~M-D-635. ~he results were classified into ln ~m b~sf~'b~e "combustible", "slow-burning" and "i~Q-h~iblo", in which "slow-burning" and "incombustible" were evaluated as "pass" and "combustible" as "failure". Impact strength (Izod impact strength) and heat distortion temperature were measured according to JIS (Japanese Industrial Stan-dard)-6871. Flow propertJ (fluidity) was measured by an extruded amount of the sample resin by means of Koka flow tester (supplied by Shimazu Seisakusho, Japan) with a load of 150 kg/cm and nozzle Ool cm~xlOcm and at a temperature of 200C. The properties of the resulting resinous compositions are shown in the following ~able 1.
In ~able 1~ the underlined numerals denote the va]ues which do not satisfy the standards of the present resi-nous composition. ~he resinous composition which satis-fies fire retardance, impact resistance, heat stability and flow property simultaneously can be readily obtained according to the present invention by blending AB~ resins with the vinyl chloride resin compounds. When HCA is not employed, the composition is inferior in flow property (cf. comparative examples 4 and 5). ~he flow property itself may be enhanced by addition of a plasticizer such as DOP (dioctyl phthalate) to the composition, but heat ~ ~ distor~f/0,1 ter~pera~ e stability is markedly lowered (cf. comparative examples 6 and 7). ~he data of the examples are clearly superior to those of the comparative examples.
~ he mixed resin compositions in which the amounts of vinyl chloride resin compounds are less than 20 % by weight are not satisfactory in the degree of fire retard-ance (cf. comparative examples 1 and 2). ~he mixed resin compositions in which less than 30 % by weight of ABS
resins are contained are inferior in both impact strength ~ 5rort/on ~e~p ercL ~re and heat ntabilit7 (cf. comparative example 3)0 _ _ ... ..... .

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~ ~ ~ __ Examples of the Invention Comparative _ amp es ~_ . . . _ Examples 11 - 13 ~ hese examples show the effects obtained by in-corporating, to the resinous compositions of Examples 9 ~ rlade ~1a~e~
and 10, an MBS resin (B~A IIIs~supplied by Kureha Kagaku Kogyo) sold as an impact modifier for vinyl chloride resins or a commercially available chlorinated polyethy lene (ClPE), in the following ~able 2.
Impact strength of the resinous composition can be readily be enhanced without impairing fire retardance, heat stability and fluidity thereof, as shown in the Table.

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~ I Examples of ~ ! Invention .

Examples 14 - 17 and Comparative Examples 8 - 10 ~ he resinous composition of Example 4 was mixed with the ordinary low-molecular fire retardant additives, namely antimony trioxide (Sb203) or hexabromobenzene (C6Br6). ~he results are sho~n in ~able 3. Fire retar-dant effect was further e~hibited by addition of a small amount of the fire retardant additive to the resinous composition of the present inventionO Moreover, the fire retardant additive gave no substantially adverse effec-t to the other properties of the resinous composition.
On the other hand, a mixture of ABS resin alone and a small amount of the fixe retardant additive (Sb203) scarcely exhibited a fire retardant effect, and impac-t R 0,4~er/'or~zf~/, L~ strength thereof was markedly dctrior.atcd. ~he results are also shown in ~able 3 (comparative examples 8, 9, and 10) .

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~3 0 ____ 1 0 ~ Examples of ! Comparative I ~ the Invention I Examples Examples 18 - 20 ._ Combinations of the following graft polymers prepared by polymerizing styrene, acrylonitrile and me-thylmethacry-late on a butadiene-based polymer, and a styrene-acrylo-nitrile copolymer (A~ resin) were chosen as ABS resins to be used in the present inventionO
Graft Polymer (1):
To a latex containing 65 parts by weight of a copoly-mer rubber of an average particle size of 0.3 ~ consisting of 90 % by weignt of butadiene and 10 % by weight of styrene were added a monomer mixture consisting of 27 parts by weight of styrene containing 00035 parts by weight of diisopropylbenzene hydroperoxide and 0.075 parts by weight of divinylbenzene and 8 parts by weight of acrylonitrile, and 10 parts by weight of distilled water containing 0.0175 parts by weight of formaldehyde sodium sulfoxylate. ~hen, polymerization was carried out continuously for 7 hours at a temperature of 60C.
~ o the latex thus obtained were added 0O5 parts by weight each of ditertiarybutyl paracresol and dilauryl-thiodipropionate, and thereafter the latex was subjected to coagulation with an aqueous solution of hydrochloric acid, washed with water, dehydrated and dried at 60C, whereupon a graft polymer (ABS resin) was obtained in powder form. ~he polymerization yield was approximately 100 %.
Graft Polymer (2):
Graft polymer (2) (MB~ resin) was produced in the same manner as graft polymer (1) except that 27 parts by weight of styrene and 8 parts by weight of acrylonitrile polymerized on the rubber polymer in graft polymer (1) were substituted by 17.5 parts by weight of styrene and 17.5 parts by weight of methyl methacrylate.
Graft Polymer (3) Graf-t polymer (3) (ABSM resin) was produced in the same manner as graft polymer (1) except that 27 parts by weight of styrene and 8 parts by weight of acrylonit-rile polymerized on the rubber polymer in graft polymer (1) were substituted by 1305 parts by weight of styrene, 17.5 by weight of methyl methacrylate and 4 parts by weight of acrylonitrile.
AS Resin:
The following constituents were charged into a reaction vessel and after replacement of the atmosphere therein with nitrogen, polymerization was carried out continuously for 20 hours at a temperature of 60C.
Parts b~ weight styrene 75 acrylonitrile 25 tertiarydodecylmercaptan 0.25 azobisisobutyronitrile 0.25 polyethylene oxide 0.3 methylcellulose Ool distilled water 100 The slurry obtained was dehydrated by a centrifugal separator, washed with water and dried at 80C, whereupon a copolymer was obtained in bead form.
The reduced visicosity (~sp/C) of this copolymer in dimethylformamide of a concentration of 0.4 g/dl at 30C was 0.8g/dl.
Each of the graft polymers and the AS resin thus prepared were blended with polyvinyl chloride com-pound in a dry state to produce resinous compositionsO
A stabilizer was added and samples were prepared in the same manner as Example 1, which samples were used in the respective testsO
~ he properities of these resinous compositions are summarized in ~able 4.

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lO~Z835 ~ able 2 shows that the four resin mixtures prepared by blending graft polymers and AS resin with polyvinyl chloride compositions can achieve all the objects of the present invention, iOe., low combustibility, high impact strength, heat resistance and fludity under processing conditions.
While the invention has been particularly shown and described with reference to preferred embodiments thereof, it will be understood by those skilled in the art the foregoing and other changes can be made without depart-ing from the spirit and scope of the inventionO

Claims (14)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A resinous composition having good flow property and fire retardance comprising a blend of (1) about 80 to 30 parts by weight of an ABS resin and (2) about 20 to 70 parts by weight of a vinyl chloride resin compound comprising (i) 100 to 5 parts by weight of a copolymer resin of about 0.5 to 40% by weight of a higher alkyl vinyl ether in which the alkyl group contains 12 to 18 carbon atoms and about 99.5% to 60% by weight of vinyl chloride and (ii) 0 to 95 parts by weight of a polyvinyl chloride resin.

2. The resinous composition as set forth in claim 1, in which said ABS resin comprises polymerized butadiene, acrylonitrile and/or meth-acrylonitrile, and styrene.

3. The resinous composition as set forth in claim 2, in which styrene is partly replaced by other aromatic vinyl compounds and acryloni-trile is partly replaced by methacrylates.

4. The resinous composition as set forth in claim 1, in which said ABS resin comprises about 10 to 40 parts by weight of a butadiene rubber component, about 80 to 25 parts by weight of an aromatic vinyl compound including styrene, and about 35 to 5 parts by weight of acrylo-nitrile and/or methacrylonitrile.

5. The resinous composition as set forth in claim 4, in which said butadiene rubber component is polybutadiene and/or a copolymer comprising a major part of butadiene and a minor part of monoolefinic monomers.

6. The resinous composition as set forth in claim 1, in which said ABS resin comprises (a) a graft polymer selected from the group consisting of graft polymers of acrylonitrile and styrene onto a butadiene-based polymer, graft polymers of methyl methacrylate and styrene onto a butadiene-based polymer and graft polymers of acrylonitrile, styrene and methyl methacrylate onto a butadiene-based polymer, and (b) a copolymer comprising polymerized acrylonitrile and styrene.

7. The resinous composition as set forth in claim 1, in which said alkyl group is selected from the group consisting of lauryl, cetyl, stearyl and myristyl.

8. The resinous composition as set forth in claim 1, in which said vinyl chloride resin compound consists essentially of said copolymer of a higher alkyl vinyl ether and vinyl chloride.

9. The resinous composition as set forth in claim 1, in which said vinyl chloride resin compound consists essentially of said copolymer of a higher alkyl vinyl ether and vinyl chloride and polyvinyl chloride resin.

10. The resinous composition as set forth in claim 9, in which said vinyl chloride resin is a homopolymer of vinyl chloride.

11. The resinous composition as set forth in claim 1, in which not more than about 20 parts by weight of an impact modifier for vinyl chloride resins is incorporated to 100 parts by weight of the resinous composition.

12. The resinous composition as set forth in claim 11, in which said impact modifier is selected from the group consisting of an MBS resin, a chlorinated polyethylene, and an ethylene-vinyl acetate copolymer rubber onto which vinyl chloride has been graftpolymerized.

13. The resinous composition as set forth in claim 1, in which an antimony compound is incorporated as a fire-retardant auxiliary into the resinous composition.

14. The resinous composition as set forth in claim 1, in which a fire-retardant additive selected from the group consisting of chlorinated paraffins, hexabromobenzene, tetrabromoethane and tetrabromobisphenol A is incorporated into the resinous composition.