AU623440B2

AU623440B2 - Microbiocidal compositions

Info

Publication number: AU623440B2
Application number: AU42722/89A
Authority: AU
Inventors: Lawrence Paul Grant; Nuno Maurice Rei
Original assignee: Morton Thiokol Inc
Current assignee: ATK Launch Systems LLC
Priority date: 1988-10-11
Filing date: 1989-10-09
Publication date: 1992-05-14
Anticipated expiration: 2009-10-09
Also published as: BR8905154A; IL91891A0; EP0364159A3; DK501989D0; NO894045D0; EP0364159A2; ZA907379B; KR900005873A; JPH02288801A; AU4272289A; PT91945A; NO894045L; DK501989A; NZ230806A

Description

required PHILLIPS ORMONDE AND FITZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne, Australia P17/2/83 I ,s I

AUSTRALIA

Patents Act 623440 COMPLETE SPECIFICATION

(ORIGINAL)

Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority iRelated Art: Applicant(s): 4 ft tr Morton Thiokol, Inc.

110 North Wacker Drive, Chicago, Illinois, 60606, UNITED STATES OF

AMERICA

Address for Service is: PHILLIPS ORMONDE FITZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne 3000 AUSTRALIA Complete Specification for the invention entitled: MICROBIOCIDAL COMPOSITIONS Our Ref 149386 POF Code: 1436/105577 The following statement is a full description of this invention, including the best method of performing it known to applicant(s): -1- 1 6006 0 k1.HaLijd.HL oazy P18/7/78 PHILLIPS ORMONDE FITZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne, Australia

XI

1769-34-00

PATENT

MICROBIOCIDAL COMPOSITIONS BACKGROUND OF THE INVENTION Field of the Invention S I£I t *4 4 4 I i

II

4 I I I 1

I

CI 40 °o 00 0 0 0 0 S* ft I 4. t This invention relates to homogeneous compositions comprising a carrier, a microbiocidal compound, and a solvent for the microbiocidal compound which is also compatible with the carrier.

The present invention further relates to a process for imparting microbiocidal properties to polymer compositions i° comprising adding to the polymer composition a homogeneous microbiocidal composition comprising a carrier, a microbiocidal compound, and a solvent for the microbiocidal compound.

This invention further relates to compositions comprising a homogeneous solution of a liquid plasticizer for vinyl resins, a biologically effective amount of a iicrobiocidal compound, and a solvent for the microbiocidal compound.

This invention further relates to polymer, vinyl resin, compositions comprising an admixture of a polymer and a a_0 composition containing a carrier, plasticizer, and in an amount sufficient to impart ricrobiocidal properties to the polymer composition, a microbiocidal compound dissolved in a solvent.

Prior Art It is p-esently common practice to protect polymer or plastic compositions from microbiological, bacterial or fungal, attack by incorporating microbiocidal compounds into the polymer or plastic compositions. The resulting polymer compositions prevent the deterioration of articles formed from 2o the polymer compositions which is due to microbiological attack on the polymer, the plasticizers or other polymer la 1769-34-00

PATENT

additives which are normally incorporated into the polymer compositions to impart desirable physical properties to the articles and to facilitate forming of the articles.

Many of the available microbiocidal materials are solid, and in order to incorporate them homogeneously into polymer compositions, it is necessary to first mix them with liquids which solubilize or disperse the microbiccidal materials unifor~mly arid, thereafter, mix the thus-formed liquid compositions with the polymers. Unfortunately, the Lc solubilities of many of the microbiologically active compounds in the more common solvents are quite low. Therefore, it is either difficult to incorporate a sufficiently high concentration of a microbiocidal compound with a polymer or, if a sufficiently high concentration of the microbiocidal compound can be incorporated in the polymer, an undesirably high concentration of the solvent must also be incorporated into the polymer, compromising the desirable characteristics of the polymer composition.

Attempts to solve these problems have met with varying, often limited, success. For example, U.S. Patent No.

3,288,674 issued November 29, 1966 to Yeager (reissued on J September 20, 1977 as Re. 29,409), U.S. Patent No. 3,360,431 issued December 26, 1967 to Yeager, and U.S. Patent No.

3,689,449 issued September 5, 1972 to Yeager and Wilson disclose the use of solvents having a labile hydrogen, such as phenols nonyl phenol) and C 5

-C

12 aliphatic alcohols, to dissolve microbiocidally active phenoxarsine compounds, the resulting solutions being subsequently incorporated into polymeric resin compositions. While the C 5

-C

12 aliphatic 30 alcohols were found to be useful as solvents for the phenoxarsines, their ability to aid in the incorporation of the phenoxarsines into plasticizer compositions was recognized only to a limited extent. Thus, the maximum amount of phenoxarsine disclosed as being incorporated into a plasticizer composition is only 2.5 percent by weight (based on the total weight of phenoxarsine, solvent, and plasticizer).

-2- 1769-34-00

PATENT

U.S. Patent No. 4,663,077 issued May 5, 1987 to Rei and Wilson describes the advantageous use of aryl alkanols, such as benzyl alcohol, as solvents for microbiocidal agents which are to be formulated into solutions with carriers, such as plasticizers and/or other processing aids. The patent teaches that aryl alkanol solvents, such as benzyl alcohol, increase the levels of microbiocides, particularly phenoxarsines, which can be dissolved per amount of solvent.

U.S. Patent No. 4,049,822 issued September 20, 1977 to Io Rei et al. discloses that phenoxarsines can be solubilized with glycyl phosphites or glycyl phosphonates. These phosphites and phosphonates may be used in admixture with solvents having a labile hydroxyl group, such as phenols and

C

5

-C

12 aliphatic alcohols.

SUMMARY OF THE INVENTION In accordance with the present invention, there are provided homogeneous, stable liquid compositions comprising a carrier, a solvent selected from C 5 to C 9 aliphatic alcohols and diols, and a microbiocidal compound soluble in said o- solvent wherein the microbiocidal compound is present in the composition as a solute in the solvent and constitutes greater than 2.5 percent by weight of the combined weight of the carrier, solvent and microbiocidal compound.

Also provided in accordance with this invention is a process for imparting microbiocidal properties to a polymer composition comprising adding to a polymer, in an amount at least sufficient to impart antimicrobial properties to the polymer composition, a homogeneous, stable liquid composition comprising a carrier, a solvent selected from C 5 to C 9 3o aliphatic alcohols and diols, and a microbiocidal compound soluble in said solvent, wherein the microbiocidal compound is present in the composition as a solute in the solvent and constitutes greater than 2.5 percent by weight of the combined weight of the carrier, microbiocidal compound and solvent.

3 L769-34-00 S PATZNT There are further provided in accordance with tha present invention polymer, vinyl resin, compositions comprising an admixture of a polymer and, in an amount at least sufficient to impart antimicrobial properties to the polymer composition, a homogeneous, stable liquid composition comprising a carrier, a plasticizer for the polymer, a solvent selected from C 5 to C 9 aliphatic alcohols and diols, and a microbiocidal compound soluble in said solvent, wherein the microbiocidal compound is present as a solute in the ro solvent and constitutes greater than 2.5 percent by weight of the combined weight of carrier, microbiocidal compound, and solvent.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is specifically directed to applications in which the microbiocidal compound is not tit sufficiently in a carrier, such as a plasticizer or other S",processing aid, to be provided to the resin through solution in the carrier alone. In such case, an organic solvent is used which is a cosolvent for the microbiocidal compound and ao_ the resin or a cosolvent for the microbiocidal compound and the carrier, the plasticizer. Specifically, the present invention is directed to applications in which the cosolvent is a C 5 to C 9 aliphatic alcohol or diol such as isodecyl alcohol, 2-ethyl hexanol, 2-ethyl-l, 3-hexanediol or mixtures thereof which have been found to allow the addition of relatively high levels of microbiocidal compounds to a carrier, plasticizer, and provide homogeneous, stable compositions. As used herein, the term "stable" means that the microbiocide remains dissolved in the carrier-containing 2o composition and does not precipitate or recrystallize after standing at room temperature for, 30 days, or after being subjected to several freeze/thaw cycles.

As used herein, the term "C 5 to C 9 aliphatic alcohols or diols" refers to compounds whose longest continuous chain of 4 I I 1769-34-00

PATENT

aliphatic carbon atoms has from 5 to 9 carbon atoms in it, and with one or two -OH groups being bonded to that C 5 to C 9 chain. Thus, the overall molecule may contain greater than nine carbon atoms, without departing from this definition, as long as the longest continuous chain of carbon atoms is C 5 to

C

9 An example of such a compound is isodecyl alcohol which has 10 carbon atoms overall, but only nine carbon atoms in its longest continuous chain.

Examples of the C 5 to C9 aliphatic alcohols and diols of o this invention include, but are not limited to, isodecyl alcohol (including the material commonly termed "isodecyl alcohol" which is a mixture principally of trimethyl heptanols), 2-ethyl hexanol and 2-ethyl-i, 3-hexanediol.

Examples of the types of microbiocidal compounds which may be employed in this invention include, but are not limited to, phenoxarsines (including bisphenoxarsines), and phenarsazines (including bisphenarsazines).

The microbiocidal phenoxarsine and phenarsazine compounds useful in the compositions of this invention include compounds to represented by the formulas: I i 5 i 1769-34-00

PATENT

and where X is thiocyanate, Y is oxygen or sulfur, Z is oxygen or nitrogen, R is halo or lower alkyl, and n is 0 to 3. Examples of these phenoxarsines and phenarsazines include, but are not limited to, 10,10' -oxybisphenoxarsine (QEPA); lO-thiocyanato phenoxarsine; 10, 10' -thiobisphenoxarsine; Co 10,10' -oxybisphenarsazine and 10,10' -thiobisphenarsazine.

-6 r- c 1769-34-00

PATENT

The most preferred microbiocidal compounds are the bisphenoxarsines and bisphenarsazines having the formula:

I

Y

where Y is oxygen or sulfur and Z is oxygen or nitrogen. Of these bisphenoxarsines and bisphenarsazines, the most preferred are 10,10'-oxybisphenoxarsine; 10,10'-thiobisphenoxarsine; 10,10'-oxybisphenarsazine; and 10,10'-thiobisphenarsazine.

The microbiodical compositions useful in this invention should be employed in an amount at least sufficient to impart 'I 'D microbiocidal properties to the polymer composition or material containing them. This amount can vary widely depending upon the particular microbiocidal compound employed, the other components of the polymer composition in which it is employed, the environment in which the polymer composition will function, and several other factors. The minimum amount of microbiocidal compound employed in a polymer composition is determined by what is known in the art as its Minimum Inhibitory Concentration (MIC). The maximum amount of microbiocidal compound which can be employed in a polymer o composition is determined only by the amount of microbiocidal compound which can be uniformly incorporated into a particular polymer composition without adversely affecting the physical properties of the polymer composition. In general, the polymer compositions of this invention which possess microbiocidal properties contain from about 50 parts per million (ppm) to about 10,000 ppm, preferably about 100 ppm to 500 ppm, of microbiocidal compound. Fhenoxarsine and phenarsazine compounds, the preferred ricrobiocidal compounds -7

L

1769-34-00

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in accordance with this invention, are used at levels of between about 100 and about 5,000 ppm (based upon the total weight of the polymer composition) and preferably between about 300 and about 1,000 ppm.

The microbiocidal compositions of this invention preferably contain much more microbiocidal compound than would be necessary simply to impart the desired microbiocidal properties to them. These compositions preferably contain large amounts of microbiocidal compound because they are (o advantageously employed as "concentrates" to produce polymer compositions which have lower concentrations of microbiocidal compounds, but still have the desired degree of microbiocidal activity. For example, a carrier-containing liquid composition may contain about 5% to about 10% microbiocidal compound, but may in turn, be used to prepare a polymer composition containing only 100 to 500 ppm microbiocidal compound.

The microbiocidal compositions of this invention, °o comprising a carrier, a solvent selected from C 5 to C 9

S

0 aliphatic alcohols and diols such as isodecyl alcohol, 2-ethyl 4 hexanol, 2-ethyl-l, 3-hexanediol or mixtures thereof, and a microbiocidal compound, may be employed as additives for polymer compositions to impart microbiocidal properties to the polymer compositions. Examples of suitable carriers include, but are not limited to, plasticizers, and lubricants.

Specific examples of carriers include, but are not limited to, 4 typical plasticizers such as tricresyl phosphate, dipropylene o glycol dibenzoate, diphenylcresyl phosphate, epoxidized soya, o epoxidized tallate, dioctyl azelate, di(2-ethyl hexyl) .o 30 phthalate, alkyl aryl phosphates, diisobutyl phthalate, 0 diisodecyl phthalate, hydrogenated methyl rosin ester, n-octyl n-decyl phthalate, mixed n-alkyl phthalates, butyl benzyl A1' 0 phthalate, di-n-octyl phthalate, di-n-decyl phthalate, 3,4-epoxycyclohexyl methyl 3,4-epoxycyclohexane carboxylate, trioctyl trimellitate and low molecular weight polymeric plasticizers, such as Paraplex G-300 plasticizer sold by Rohm Haas Co., and the like. Of these plasticizers, di(2-ethyl 8 1769-34-00

PATENT

hexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate and epoxidized soya are preferred. Other polymer processing aids useful as carriers in accordance with this invention include, but are not limited to, polypropylene glycol; 1,4-butanediol; and methyl ethyl ketone. The compositions of this invention may be added either directly to the polymer composition or they may be first incorporated into an additional amount of carrier, and then incorporated into the polymer composition. When the latter manner is chosen, the to carrier may be any of a variety of materials, including the carriers identified above, which are compatible with the polymeric resin and microbiocidal composition, the microbiocidal compound does not precipitate or otherwise separate from the cosolvent when incorporated into a polymeric resin along with the carrier.

It is generally a problem to solubilize sufficiently high a concentrations of commonly used microbiocides in solvents, and S" have the resulting solution remain stable when added to a a .t carrier, plasticizer. Generally, the solvent used to D o carry the microbiocidal compound into the carrier-containing concentrate composition and into the polymeric resin serves little or no beneficial function in the final polymeric composition and may even be detrimental if present in too high a concentration. The concentrate composition should contain the correct amount of microbiocide so that when the carrier, plasticizer, is employed at optimal amounts, the carrier-containing concentrate composition provides the correct amount of microbiocidal compound to the end-use polymer composition. At the other extreme, a solution should S' so not be too highly concentrated in microbiocidal compound, lest mixing problems be encountered; however, with the case of most microbiocides, obtaining a sufficiently high concentration of microbiocides is the major problem. For example, using solvents such as nonyl phenol, it was, heretofore, difficult to provide concentrate compositions which contained more than 2% OBPA by weight. When one considers that only a given amount of any carrier, such as a plasticizer, might be 9 L i. 1 I 1769-34-00

PATENT

0q 0 0 0 4 0 0 I 00 o o S"0 0 o 0 0 006 0 0 4 O 4 a I 4 14 0 40 000 I incorporated into a polymeric composition, if such a concentrate were the only source of microbiocidal compound to the final polymer composition, the microbiocide might be incorporated into the polymer composition only at sub-optimal levels. Using solvents having aryl alkanol moieties as described above, OBPA-containing plasticizing compositions containing 5% and upwards by weight have been produced. It has now been found that using C 5 to C 9 aliphatic alcohols or diols such as isodecyl alcohol, 2-ethyl hexanol, 2-ethyl-l, 3-hexanediol or mixtures thereof as the solvent likewise allows one to prepare concentrates containing higher amounts, 5% to 10% by weight, of the microbiocide, OBPA.

High concentrations of microbiocide compounds, both in solutions and in carrier-containing concentrate compositions, are desirable in other ways too. Less material, e.g., solvent, is required. Shipping and handling cost savings are also realized because less material must be shipped and stored.

The polymers employed in the processes and products of a this invention cover a wide variety of materials. In general, they include thermoplastic and thermosetting polymers, elastomers, and other materials commonly known as "plastics".

Other organic materials, for instance, naturally occurring materials, such as natural rubbers, cellulose and the like, are considered full equivalents of the "polymers" of this invention and should be included within that term. Examples of the polymers useful in the practice of this invention include, but are not limited to vinyl resins (such as those made from vinyl chloride and/or vinyl esters), polyolefins 1o (such as polyethylene and polypropylene), elastomeric polyurethanes, nylon, polystyrene, polyesters (such as polyethylene terephthalate), polycarbonates, acrylonitrile-butadiene-styrene (ABS) copolymers, SBR rubbers, styrene-acrylonitrile copolymers, acrylic polymers, thermosetting polyurethanes (such as those used for foams and coatings), phenolic resins, silicone rubbers, natural rubber, 10 L. z ~1 1769-34-00

PATENT

EDPM polymers, cellulose and its derivatives, epoxy resins, and various latexes.

The microbiocidal compositions of this invention can be prepared by simply adding the desired amount of microbiocidal compound to the solvent, heating (if necessary) the resulting mixture to a temperature which will cause the microbiocidal compound to dissolve, and maintaining that temperature until all of the microbiocidal compound dissolves. The resulting solution can then be cooled to room temperature. In this 10 manner, stable microbiocidal solutions, those wherein no significant amount of microbiocidal compound precipitates from the solution upon cooling to room temperature, can be formed.

The carrier-containing compositions of the present invention may then be prepared by merely adding the carrier to the microbiocidal solution, prepared as described above, and mixing at room temperature until a uniform solution results.

Alternatively, all ingredients of the carrier-containing composition (microbiocidal compound, solvent and carrier) can be mixed together and heated (if necessary) until the a microbiocidal compound dissolves.

The microbiocidal compositions of this invention can be used to impart microbiocidal properties to polymer compositions. This can be done by simply adding the carrier-containing microbioeidal composition to the polymer composition by any of several convenient methods known in the art. Thus, for instance, the polymer resin can be melted and the microbiocidal carrier-containing composition added to and fit, mixed with it (as in an extruder). Alternatively, the i polymeric resin can be softened with or dissolved in a solvent 30 and the microbiocidal carrier-containing composition added to and mixed therewith.

The following examples illustrate the present invention, and are not intended to limit the invention or its scope in any manner. As used in the examples and throughout this specification, all parts and percentages are by weight unless otherwise indicated.

11 L 1 1 I 1769-34-00

PATENT

EXAMPLE 1 A solution containing 20 wt% OBPA dissolved in 80 wt% isodecyl alcohol (IDA), the percentages based on total solution weight, was prepared by mixing the ingredients and heating the resulting mixture to about 220 0 F and maintaining that temperature until all of the OBPA dissolved. The resulting solution was stable, but crystallized after 24 hours. Portions of this solution were then used to prepare carrier-containing compositions containing 5 wt% OBPA using the carriers (plasticizers) listed in Table 1 below wherein the numbers indicate the weight percent of each ingredient based on total composition weight. These carrier-containing compositions were prepared by diluting the OBPA/IDA solution with the carrier and mixing the resulting product.

TABLE 1 00 4 of Silicone SSample OBPA IDA DINP DO2 DIDP S-160 ESO S-711 Oil o oa S1 5 20 2 5 20 S3 5 20 4 5 20 5 20 6 5 20 7 5 1 S DINP is diisononyl phthalate S DOP is di(2-ethyl hexyl) phthalate, sometimes called dioctyl phthalate DIDP Is diisodecyl phthalate S-160 is butyl benzyl phthalate 6 BSO is epoidized soya S-711 is a mixture of C 7 C and C11 branched phthalates.

0o The stability of Samples 1-7 was determined with the results indicated in Table 2.

-12

V

i i_ 1769-34-00

PATENT

Sample 1 2 3 4 \d 5 6 7 Carrier

DINP

DOP

DIDP

S-160

ESO

S-711 Silicone Oil Immediately After Preparation

OK

TABLE 2 After 1 Day At Room Temp

OK

After 1 Nonth At Room Temp

OK

NG*

After 5 Freeze/Tha- Cycles

OK

NO

NO unstable, precipitate formed @4

I

4 44 4 I o 4 o 441 44 4 41 04; 444 All of the samples exhibited good stability throughout the room temperature aging and freeze/thaw cycling with the exception of Sample 7. That sample, which employed silicone oil as the csrrier, was not as stable as the other samples after long term room temperature aging and freeze/thaw cycling.

EXAMPLE 2 Additional carrier-containing compositions were prepared in the manner described in Example 1 using the ingredients and amounts indicated in Table 3 below wherein the numbers indicate the weight percent of each ingredient based on total composition weight.

4 I 44 4 44 «o a a 04 0444 o a« a t I t t 4 4 13 1769-34-00

PATENT

TABLE 3 DOP DIDP Sample OBPA IDA S- 160 11.7 11.7 11.7 11.7 83.3 87.5 83.3 87.5 83.3 87 83.3 87.5 4* 4 4 9* 4 #4 09 4 4' 4.

*4 09 q~ 4 99 94 4 44 *1S4 '4 23.3 23.3 23.3 23.3 66.7 66.7 66. 7 66. 7 41 44 4 '4 r i 4 4 '.4 441.

4 4 1 2 -r 9 The stability of each of Samples 8-31 was determined with the results indicated in Table 4 below.

14 r r r r- L L t I r L P cZ OIe O OD O O O 0 0000I D O D J O ~610 O r I II O I I D IIO r 411 411 TABLE 4 Stability For 5% OBPA Formulation Immediately after Sample Carrier Preparation After 1 On Day at Cooling Room Tomp

ESO

DOP

DI DP S-160

ESO

DOP

DIDP

S-160

ESO

DOP

DIDP

S-160 After 1 Month At Room Temp After 5 Freeze/ Thaw Cycles 30 Days Heat Aging at 55 0

C

Good Stability Poor Stability recrystalization of OBPA t-3 Li

C--

z i 4.

I

o 4-I L TABLE 4 Stability For 10% OBPA Formulation Immediately after Carrier Preparation Af tar 1 On Day at Cooling Roam Tamp sample

ESO

DOP

DI DP S-160

ESO

DOP

DI DP 5-160a

ESO

flOP

DIDP

C

Good Stability Poor Stability recrystalization of OIPA 0) C3 -3 1769-34-00

PATENT

The above data indicates that most of the samples were stable. Some of the samples were not stable when relatively low amounts of IDA were employed, but were stable when the amount of IDA was higher, Sample 17 vs. Samples 9 and 13; Sample 29 vs. Samples 21 and 25; and Sample 30 vs. Samples 22 and 26.

EXAMPLE 3 This example illustrates carrier-containing compositions of the present invention which contain microbiocides other S than OBPA. These compositions were prepared in the manner described in Example 1 using the ingredients and amount indicated in Table 5 below wherein the numbers indicate the Sweight percent of each ingredient based on total composition S' weight.

TABLE S, Sample Biocide Biocide IDA Plasticizer 32 10-CPA 5 20 33 RH-948 5 20 34 Myacide AS 5 20 14 10-CPA is RH-948 is n-cyclohexyl-4, 5-dichloro-4-isothiazolin-3- Myacide AS is 90% 2-bromo-2-nitropropane-l,3-diol, 10% inert ingredients I I i t The stability of Samples 32-34 was determined, and the results are indicated in Table 6 below.

S1 17 L A A. a A

A

TABLE 6 Immediately of ter Biocide Carrier Preparation Af tar 1 On Day at Cooling Roam Tamp After 1 Month At Room Temp After 5 Freeze/ Thaw Cycles 30 Days Heat Aging at 55 0

C

Sample 32 3 34 10-CPA RH-949 Myacide

AS

DI DP DI DP DI DP =Good Stability 00- Poor Stability recrystalization Lo C1) 1769-34-00

PATENT

The above results illustrate that not all microbiocides are soluble/stable in IDA to the same extent. Thus, 5% (a compound closely related to OBPA) would not dissolve in IDA, and Myacide AS was not stable in the carrier-containing composition at the 5% level. However, under the same conditions, 5% microbiocide and 20% IDA, RH-948 was very stable.

COMPARATIVE EXAMPLE A This example illustrates carrier-containing compositions to which were prepared from a 20% concentrate of OBPA in dodecyl phenol instead of IDA. These compositions were prepared in the manner described in Example 1 using the ingredients and amounts indicated in Table 7 below wherein the numbers refer 4 to the weight percent of each ingredient based on total composition weight.

I 9

(I

I o t 1769-34-00

PATENT

TABLE 7 OBPA DOP Aif'R.

SilIicone Oil Sample ESO DINP DIDP S-711 DO? S-160 a

J

K

Ii

N

4 4 4 4 4,* 4± 4' 4, 44 4 ,4 4 95 95 95 4 A 4tt 4 14f The stability of the 20% concentrate solution and Samples A-U was tested with the results indicated in Table 8 below.

20 7- 1769-34-00

PATENT

TABLE 8 20% OBPAIDDP Concentrate Solution Stability Immediately After Preparation

OK

Af ter 1 Day at Room Temp

OK

Af ter 30 Days at Room Temp

OK

Af ter 5 Freeze/thaw Cycles

OK

Carrier-containingz composition stability Immediately After Carrier Preparation

I

h> Sample OBPA r 4- 44 A 5 ESO a 5 DINP C 5 Silicone Oil D 5 DIDP OK E 5 S-711 F 5 DOP G 5 S-160 H 2 ESO 1 2 DINP J 2 Silicone'~ OK Oil K 2 DIDP L 2 S-711 OK M 2 DOP OK N 2 S-160 OK After 1 Day Room Temp

NO

After After 30 Days 5 Freeze/Thaw Room Temp Cycles 21 8aI I 1769-34-00

PATENT

Immediately After After After After 1 Day 30 Days 5 Freeze/Thaw Carrier Preparation Room Temp Room Temp Cycles Sample OBPA 0 1 ESO P 1 DINP Q 1 Silicone Oil OK R 1 DIDP S-711

DOP

S-160 The above data illustrates that, while the concentrate solution of OBPA in dodecyl phenol is stable, with only a few exceptions, the carrier-containing compositions are unstable, even at the 1% OBPA level.

COMPARATIVE EXAMPLE B Additional materials were tested in the same manner described in Comparative Example A using the ingredients and amounts indicated in Table 9 below wherein the numbers refer to weight percent of each ingredient based on total composition weight.

a a 0 a S 22 1769-34-00

PATENT

TABLE 9 Sample OBPA MPBA Polymeg W-430 MPT EPAL DIDP S-160 ESO 0 0 1A 2A 3A 4A 6A lB 2B 3B 4B 6B

'C

2C 3C 4C 6C

ID

2D 3D 4D 6D 1E 2E 3E 4E 6E MPBA is m-phenoxy benzyl alcohol Polymeg is Polymeg 1000 poly (oxytetramethylene) diol W-430 is Weston 430 Phosphite C which is tris(dipropyleneglycyl) phosphite MPT is m-phenoxytoluene EPAL is a mixture of high straight chain alcohols.

The stability of the carrier-containing compositions of 4o Table 9 and the 20% concentrate solution was tested with the results indicated in Table 10 below.

23- 10 1769-34-00

PATENT

TABLE QEPA Concentrate Solution Stabilitv Immediately After Prepar~at .OrL After After 5 2 Weeks Freeze/Thaw Room Temp Cycles Solvent Af ter 30 Days in Oven At 55 0

C

OK

NG

MPBA

Polymeg W-430

MPT

to EPAL 41 4 11

C

14 4, 4 4 ftC (C I o 44 4 *4 0444 .4,4 C;~4 1 4 1444 414444 4 4444 4 4 4 24 __j 1769-34-00

PATENT

Carrier-Containing Composition Stability Immediately After Prep arat ion Af ter 2 Weeks Room Temp After 5 Freeze/Thaw Cycles Af ter 30 Days in Oven At 55 0

C

Sample

IA

2A 3A 4A 6A

(MPBA)

1B 2B 3B 4B 6B) 2C}

(POLYMEG)

ft If 4.4 4. V 4 ft 4. 4 4. 1 4441 (W-430)

ID'

2D 3D 4D 6D)J 1E 2E 3E 4E 6E

(MPT)

(EPAL)

14 4.

4. 4 V V I As can be seen from Tables 9 and 10, only the compositions employing m-pherioxybenzyl alcohol were stable through all of the tests.

25 12 1769-34-00

PATENT

EXAMPLE 4 Carrier-containing compositions were prepared in the manner described in Example 1 using the ingredients and amounts indicated in Table 11 below wherein the numbers indicate the weight percent of each ingredient based on total composition weight.

TABLE 11

H

BB 5 20 Ii While the 20% OBPA concentrates used to prepare samples AA and BB showed considerable OBPA crystallization upon cooling, the carrier-containing solutions were stable, even after freeze-thaw cycling.

COMPARATIVE EXAMPLE CC A solution was prepared in accordance with Example 4, except that 1-decanol was used as the solvent. The 20% OBPA concentrate showed considerable crystallization upon cooling, 4> and the carrier-containing composition showed some OBPA crystals after 1 freeze-thaw cycle and after 7 days room temperature aging. This demonstrates that when the longest continuous chain of carbon atoms in the solvent compound exceeds nine carbon atoms, the stability of the concentrate decreases.

26 -1

Claims

1. A homogeneous, stable liquid composition for use in blending with a plastic material comprising a plasticizer for the plastic material, a solvent selected from the group consisting of a branched chain aliphatic alcohols and diols having eight to ten carbon atoms and 10,10' oxybisphenoxarsine present in the composition as a solute in the solvent and constituting greater than 2.5 percent by weight of the combined weight of the plasticizer, solvent and 10,10' oxybisphenoxarsine.

2. A composition according to claim 1 wherein the solvent is isodecyl alcohol.

3. A composition according to claim 1 wherein the solvent is 2-ethyl hexanol.

4. A composition according to claim 1 wherein the solvent is 2-ethyl-l, 3-hexanediol.

5. A composition according to any of claims 1 to 4 wherein the plasticizer is a plasticizer for a vinyl resin.

6. A homogeneous, stable liquid composition for use in protecting plastic products from biological attack comprising a plasticizer for the plastic product, a branched chain aliphatic alcohol or diol solvent having eight to ten carbon atoms and present in an amount of at least 5 percent by weight of the total composition, 10,10' oxybisphenoxarsine present in the composition as a solute in the solvent.

7. A composition according to claim 6 wherein the solvent is isodecyl alcohol.

8. A composition according to claim 6 wherein the solvent is 2-ethyl hexanol. 1.39

9. A composition according to claim 6 wherein the solvent 27 is 2-ethyl-i, 3-hexanediol.

A composition according to any one of claims 6 to 9 whefein the 10,10' oxybisphenoxarsin, constitutes from five to ten percent by weight of the composition.

11. A composition according to claim 1 or 6 substantially as hereinbefore described with reference to any one of the examples. DATED: 17 February, 1992 PHILLIPS ORMONDE FITZPATRICK S Attorneys for: MORTON THIOKOL INC. SI e a e o aa o 0 o 39 8735N WDN 28