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1 Monsanto {Chemicals
AROCLOR 1254
Apr
CO-PLASTICIZER WITH DOP FOR VINYL ORGANOSOLS AND PASTES
1m
Monsanto Technical Bulletin No. P-I34
Monsanto Chemical Co., St. Louis, Mo. November 1, 1948
Aroclor 125*1* (chlorinated biphenyl) Is used commercially as a co-plastlclzer vlth DOP (dioctyl phthalate) in vinyl organosols and pastes because Aroclor offers the following advantages:
1. Attractive reduction in costs.
2. Aroclor Is a superior pigment grinding and pigment dispersing medium.
3. Incorporation of Aroclor 1254 markedly reduces the flammability or the finished plastic.
4. Aroclor offers outstanding electrical properties.
5. Aroclor offers toughness and strength and in other respects the over-all qualities of the plastic such as "hand", flexibility and gloss are maintained.
6. Aroclor 1254 resists attack by biological in fluences .
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HONS 079940
I. INTRODUCTION
Polyvinylchloride organosols are dlsperisons of the plastics resin in plasticizer and solvent-diluent mixtures. Organo sols are high in solids content and therefore overcome expen sive solvent loss and multiple coating operations associated with the older solution type of coating methods.
A further step leading to almost complete elimination of sol vents is the use of plastlsols or pastes which are dispersions of the vinyl resin in the plasticizers. Such pastes are par ticularly advantageous for coating paper and other materials where the use of Inflammable solvents is prohibitive and a single pass coating operation is desired.
Organosols are used to make free films for shower curtains, rainwear and to coat fabrics used for upholstery, etc. Plastisols are especially useful for coating paper in making draperies, table cloths,etc.
This bulletin Indicates the advantages of using Aroclor 1254 as a oo-plasticlzer with dioctyl phthalate in vlnylchloride organosols or pastes. It has been found feasible to replace as much as 50 percent of DOP with Aroclor 1254. Since Aroclor is substantially less expensive than DOP or the vinyl resin, this practice offers attractive economies. It also offers substantial Improvement in the flame resistance and electri cal qualities of the plastic without altering its other de sirable physical qualities. Moreover, Aroclor 1254 is out standing as a medium for grinding and dispersing the pigments used in the coating.
II. PREPARATION
a. Grinding the Pigments:
For aesthetic reasons pigmented organosols are often required and the pigments are ground on a three-roll mill. We strongly recommend Aroclor 1254 as an unusually good grinding and dis persing medium for this purpose and believe it to be far superior in this respect to other plasticizers commonly used in organosols. The finished pigment grind is added to the main organosol formu lation where allowance should be made for the Aroclor 1254 plasticizer added as a component of the pigment grind.
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b. Grinding the Organosol:
A conventional type ball mill Is used to grind the organosol. Unless the mill Is water cooled, it Is necessary to use flint pebbles Instead of steel balls to grind the dispersion because the steel balls tend to build up heat, resulting In undesirable thickening of the organosol. It Is the concensus that the temperature during the grinding should not exceed 110F,,
Although variations may be used in the order of adding the organosol ingredients to the mill, a suggested order is to add first the solvent-diluent mixture. Xylene Is frequently used as the solvent and Apco or similar thinner as the diluents. Next the Aroclor 1254-DOP plasticizer combination Is added and finally the vinyl resin.
The organosol is ground until a uniform paste Is formed. Then the Aroolor 1254-pigment grind Is added and the ball milling is continued until the final suspension is uniform. While the time of grinding will vary, usually 18 to 24 hours is sufficient.
III. FORMULATIONS
Organosols usually require special adjustments in formulating to accomodate the working characteristics of the specific use applications. Accordingly, the following formulation is given
only to indicate a starting point in making an organosol for free film or coating work. It is a white pigmented product based on the use of 60 percent solids and 40 peroent solventdiluent mixture.
Ingredients
Organosol
Film Solids
Polyvinylchloride (VYNV-3) Aroclor 1254 Dloctyl phthalate
Victor Stabilizer 53 or 85 Pigments* Xylene
Apco Thinner
33 % 7.2 8.4
0.6 10.8 25.0
15.0
55 * 12 14
1 18
-
-
100 %
100 %
Titanium dioxide, basic lead sulfate and basic lead carbonate.
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Referring to the working qualities of the organosol, Aroclor 1254 acts very similarly as DOP. Both materials are not strong solvents for the vinyl at room temperature but be come active solvents at the elevated temperature used to fuse the organosol.
Aroclor 1254 is more viscous than DOP and may not be quite as strong In plasticizer action. Therefore, In uBlng com binations of Aroclor 1254 and DOP, It may be desirable to adjust the xylene-Apco thinner ratio to use slightly larger amounts of xylene than is the case when DOP plasticizer is used alone. Where stronger solvent action Is required rela tively small amounts of dilsobutyl ketone or methyllsobutyl ketone may be used with the thinner.
In some applications it may be possible to use the Aroclor 1254-DOP plasticizer combination in larger amount than is the case when DOP Is used alone as the plastioizer. This practice offers additional economies because the Aroclor is substantially less expensive than DOP or the vinyl resin. This praotioe also reduoes the amount of solvent and thinner and frequently the solvent- thinner ratio to total solids Is about 30 to 70.
IV. APPLICATION
a. Coatings
The organosol film Is substantially discontinuous and can be applied very heavily using the same equipment commonly used for any other spread coating. In coating work, the first coat should be tight (2 to 3 dry ounces) to get good adhesion, but subsequently as much as 8 to 12 dry ounces per running yard may be applied in a single pass.
b. Drying:
The ooating is dried at 180F. to 250F., using regular drying equipment.
o. Fusing;
Fusion will not take place below 350F. and the most common
fusing methods are to apply temperatures of 350P. to 4ooP.
from three to five minutes, or 400F. to 500F. for one minute or less. The only time required at the fusing temperature Is that necessary to bring the film to the fusing point; In many cases one minute or less is sufficient. To prevent discoloration of the film and weakening of the fabrio, heat in excess of that required for fusing should be avoided. How ever, the highest practical fusing temperature should be used.
4.
MCNS Q79S43
Hot air la the most common source of heat but Infra-red Is also used and direct contact vith hot surfaces Is effective. Familiar types of Installations are gas-fired ovens, super heated steam, electric colls, strip heaters. Infra-red lights and heated cylinders.
Although Aroclor 1254 Is noneombustlble at the fusion tem peratures, vapors from other plasticizers and especially residual solvent are Inflammable and accordingly the fusing chamber equipment should not provide a source of ignition.
In light of the elevated temperatures used during fusion. It is pointed out that vapors which may be emitted when Aroolor 1254 Is heated to high temperatures bear a degree of toxicity and should not be breathed.. It is presumed that the organosol fusion Is carried out In a closed system pro vided with suction fans to remove vaporB, which precludes workers from coming In contact with them. The vapor pressure of Aroclor 1254 Is relatively low and the values are given at 100*, 350, 400*, and 450"F. as 0.00006, 4, 10 and 30 mm. Hg., respectively.
V. DECORATION
a. Embossing:
Either a flat plate or a roll press may be used for embossing before or after fusion. Care should be taken to avoid cutting through the coating if the embossing Is done before fusion since the film is weak at this stage. The time of the embossing operation Is usually 2 to 5 seconds at 160F. to 200CF.
b. Stenoilllng:
Silk screen stencilling or printing must be dene before fusing, and the drying time of the printing Ink must be slow enough to avoid drying out on the screen, yet fast enough to permit re printing with other colors In a reasonable time.
VI. PROPERTIES OF THE FREE FILM OR COATINGS
a. Dermatology:
A free film made up of polyvinylchloride containing about 12 per cent by weight of Aroclor 1254 (about 25 parts of Aroclor 1254 based on 100 parts of vinyl resin used) and a similar amount of diootyl phthalate along with standard white pigments such as titanium dioxide was found free from Irritating or sensitizing
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the skin In accordance vlth standard skin patch tests. Moreover, similar studies made vlth Aroclor 1254 alone Indicate that thlB plasticizer is neither a skin Irritant nor sensitizer. While this Indicates safety In using Aroclor 1254, ve are not de veloping use of this plasticizer for items such as baby pants made from plastics materials.
b. Vaporization Rate of the Plasticizer:
The vaporization rates of Aroclors 1248, 1254 and 1260 compare most favorably vlth the similar values for DOP and other vinyl plasticizers selected for comparison because of their known low vaporization rates. This is indicated In the follovlng table:
Plasticizer
Surface Area cm2______ _
Vaporization Rate gms/ornyfar ,/100* C.
Aroclor 1248 Clorafih 42-3 Flexol-DOP, dloctyl
phthalate
Dutrex 25 Aroclor 1254 Dutrex 20 Aroclor 1260
12.28 12.28
12.28 12.28 12.28 12.28 12.28
0.000152 0.000126
0.000117 0.000087 0.000053 0.000016 0.000009
c. General Film or Coating Qualities:
From reliable sources In the trade using Aroclors with dioctyl phthalate to plasticize organosols, it Is Indicated that the light stability and heat stability of the free films and fabric
or paper coatings compare most favorably vlth the similar values where DOP is used as the only plasticizer.
Usually Victor stabilizer 53 or 85 is used to Improve light stability of the vinyl plastic. Basic lead carbonate, sulfate and silicate are commonly used as the heat stabilizers. Such properties as "hand", toughness, abrasion resistance, flexibility
and gloss of the films and coatings derived from the Aroclor 1254-DOP plasticized organosols seem to compare most favorably vlth the similar qualities of the vinyl plastic containing DOP
alone.
The use of Aroclor results in a substantial Improvement in fire resistant qualities of the plastic. A vinyl composition
plasticized vlth 50 parts of DOP showed a flame-out time of
6. HONS 079945
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75 seconds, whereas a similar plastic UBlng a 50-50 mixture of Aroclor-DOP at 80 pcirts plasticizer shoved a flame-out time of only 2 to 3 seconds.
Aroelors are noted for their excellent electrical qualities. Vinyls plasticized with Aroclor-DOP combinations have very good eleotrical qualities and are somewhat better In this respect than similar plastics prepared with DOP alone.
Another point worthy of mention Is that Aroelors are not susoeptlble to attack by fungi and have a pronounced repelling action against soil mites Including termites. These factors are important vhere the finished plastic Item must resist attack by microorganisms.
VII. SAVINGS ACCOMPLISHED BY USING AROCLOR 1254
IN COMBINATION WITH DOP
The following specific gravity values and selling prices (car lot quantity) of the various materials were used In making the cost calculations:
Material
3p. Q.
Selling Prlce/Lb,
PVC (VYNV) Aroolor 1254 DOP
1.35 1.54
0.980
$ 34 .18 .43
Comparative costs are given In terms of a cubic foot of the plastic material including only the vinyl resin end plasticizers.
The saving possible by using various amounts of Aroclor 1254 In combination with DOP as compared with the use of 50 parts
DOP per 100 parts resin are given:
Plastic Composition
Cost/Cu. Ft.
Savlng/Cu. Ft.
1) 50 parts DOP - 100 parts resin
$ 27.68
2) 50 parts (50-50 Aroclor 1254-D0P)-100 parts resin
26.53
$ 1.15
3) 70 parts (50-50 Aroclor 1254-D0P)-100 parts reBin
26.07
1.61
4) 70 parts (60-40 Aroclor 1254-DOF)-100 parts resin
25.74
1.94
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VIII. ADVANTAGES OP USING AROCLOR 1254 IN COMBINATION WITH DOP
1. Depending on the plasticizer ratios used as Indicated above, It Is possible to save from $1 to $2 per cubic foot of plastic.
2. Aroclor 1254 offers superior pigment grinding and pig ment dispersing qualities in preparing the organosol.
3. The use of Aroclor 1254 In these plastics markedly re duces their susceptibility to burning.
4. Aroolor offers outstanding electrical properties and resistance to organism attack.
5. Aroclor offers toughness and tensile strength and in other respects the over-all qualities of the plastic Buch as "hand", flexibility and gloss are maintained.
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The Information contained In this bulletin Is to our best know ledge true and accurate, but all recommendations or suggestions are made vithout guarantee, since the conditions of use are be yond our control. Monsanto Chemical Company disclaims any liabili ty inourred In connection with the use of these data or suggestions. Furthermore, nothing contained herein shall be construed as a recommendation to use any product in conflict with existing patents covering any material or Its use.
MONSANTO CHEMICAL COMPANY St. Louis 4, Missouri
New York-Chlcago-Boston-Birmlngham-Charlotte-Cincinnatl-Detrolt Cleveland-Phlladelphia-Los Angeles-San Franclsco-Montreal
PGB/rh
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