US2857347A - Paint composition containing vehicle comprising vinyl toluene-siccative oil copolymer and nondrying alkyd resin - Google Patents

Description

United States Patent '0 John W. de Groot, Jr., and Burt F. Holferth, Manheim Township, Lancaster County, Pa., assignors to Annstrong Cork Company, Lancaster, Pa., a corporation of Pennsylvania N Drawing. Application June 20, 1955 Serial No. 516,776

7 Claims. (Cl. 260-22) This invention relates generally to felt. base floor coverings. More particularly, the invention relates to an improved felt base floor covering having a decorative wearing surface of a Vinyl toluene modified siccative oil and a nondrying alkyd resin. Still more particularly, the invention relates to a paint composition having a vinyl toluene modified siccative oil as the principal oil vehicle and containing a nondrying alkyd resin.

Felt base floor coverings are well-known to the art, and generally speaking, they comprise a saturated felt backing, a seal coat, and a paint film which serves as both a decorative and wearing surface. One widely used method of producing such floor coverings involves the steps of face-coating a saturated felt sheet with a coating paint by means of a knife or other suitable apparatus to provide what is known in the art as a seal coat. Following the application of the seal coat, the material is passed through a block printing apparatus. The blocks are dipped into a container of decorative material and various designs are applied by means of the blocks to the coated felt base. Following the application of the decorative coating, the material is suspended in stoves to dry the paint film. The paints employed because of the manner in which they are applied are generally called print paints; and in the art the goods are known as printed felt base goods.

Various coatings have been used for decorating-the surface of a seal coated saturated felt. Generally speaking, these coatings are conventional print paints containing the desired color pigment, and a drying oil-resin type vehicle. These drying oil-resin-type vehicles have found wide use in the production of printed felt base goods.

More recently, however, it has been found that the use of a siccative oil modified with vinyl toluene, and sometimes additionally with divinyl benzene, can serve as a useful vehicle in print paints. One of the primary advantages of these vinyl toluene modified siccative oil vehicles is that the rate of cure may be substantially enhanced over that of the usual drying oil-resin type vehicle. Other properties, such as abrasion resistance and resistance to solvents and alkali, remain substantially unimpaired. For these reasons, the vinyl toluene modified siccative oil vehicles are of increasing interest in the art.

These vehicles, however, generally suffer from the shortcoming that the final cured films are too brittle for use on felt base floor coverings. Since felt base floor coverings are generally stored in rolls after manufacture and unrolled at a later date when used as a floor covering, the decorative wear-resistant layer must possess a certain degree of flexibility to be useful. The straight vinyl toluene modified siccative oil vehicles, even when further modified with divinyl benzene, have not yielded films of sufficient flexibility to serve as a vehicle in print paints.

ice

The addition of plasticizers has not cured the situation, since plasticizer addition generally inhibits the rate of cure and at the same time causes bloom on the surface of the film.

Accordingly, it is the primary object of the present invention to present a paint composition having a vinyl toluene modified siccative oil as the principal oil vehicle and which possesses in the form of cured films the necessary flexibility to serve as the decorative wear-resistant layer on felt base goods, while at the same time preserving the other properties necessary in such layers.

This object has been achieved in a surprisingly effective manner. The invention contemplates a paint composition comprising filler, pigment, solvent, and a vehicle comprising vinyl toluene modified siccative oil and a nondrying alkyd resin. The nondrying alkyd resin is the reaction product of a nondrying glyceride oil, a polyhydric alcohol, and an aromatic dibasic acid.

It is completely unexpected that the addition of a certain non-drying alkyd resin to the vinyl toluene modified siccative oil vehicles known in the art would bring about the desired flexibility in films formed from compositions containing the vehicle. It would be anticipated that the addition of a nondrying alkyd resin to the vinyl toluene modified siccative oil in amounts sufiicient to plasticize the oil would also substantially inhibit the rate of cure of the oil. Furthermore, it would be anticipated that the addition of a nondrying alkyd resin to the oil would cause undesirable bloom to appear in films formed from the resin. Just why these expected results do not occur in the composition of the present invention is not clear, and no attempt will be made to explain it.

The nondrying alkyd resins used in the present invention are those liquid products derived from nondrying or essentially nondrying animal or vegetable oils or their fatty acids, a reactive polyhydric alcohol, and an aromatic dibasic acid; it is understood that the aromatic dibasic anhydrides are equivalent to the acids in the pres ent invention.

As examples of the nondrying or essentially nondrying glyceride oils, there may be mentioned tallow and tallow oil, palm kernel oil, lard oil, neats-foot oil, coconut oil. and the like. The polyhydric alcohols include such substances as glycerine in its. various forms, polyglycerol, pentaerythritol, and the like. The polyhydric alcohol should have more than two hydroxyl groups in the molecule. To achieve this, mixtures of glycols and alcohols containing 3 or more hydroxyl groups may be used.

The aromatic dibasic acids or anhydrides include such compounds as phthalic, diphenic, or other polybasic or polycarboxylic aromatic acids.

The nondrying alkyd resins may be manufactured by alkyd resin procedures well-known to the industry. The t nondrying glyceride oil, for instance beef tallow, may be heated with the polyhydric alcohol, for instance pentaerythritol, to accomplish alcoholysis and then the aromatic dibasic acid, for instance phthalic anhydride, may be added to react with the unreacted hydroxyl groups. The amount of oil used should be sufiicient to give an oil length in the range of about 40-90 in the final product. The hydroxyl equivalents of the alcohol should be in 10-30% excess of the carboxyl equivalents of the acid in accordance with usual alkyd practice. Generally speaking, the nondrying alkyd resins used in the present invention will have an acid number in the range of about 0-15, preferably about 3-7, a hydroxyl number in the range of about 0-60, preferably about 15-25, and an iodine value in the range of about 0-40, preferably about 15-25.

As mentioned earlier, the vinyl toluene modified siccative oils are known in the art as paint vehicles. Vinyl toluene copolymerizes readily with linseed oil, soya oil, dehydrated castor oil, safflower oil, and tall oil and its esters. Further modification may be accomplished by introducing divinyl benzene into the reaction mass. The reaction is generally carried out by adding a mixture of vinyl toluene and peroxide catalyst to the heated oil. A variety of properties may be obtained in such vehicles by varying the relative amounts of ingredients, as well as by varying the type of oil reacted with the vinyl toluene. Nevertheless, it appears to be characteristic of a vast majority of these oils to yield films having insufficient elongation to serve as vehicles in print paints.

Films having improved flexibility and elongation properties may be obtained in accordance with the present invention by incorporating in the vinyl toluene modified siccative oil the nondrying or essentially nondrying alkyd resin described above.

A physical mixture of the modified oil and the nondrying or essentially nondrying alkyd resin may be used. Thus, the nondrying alkyd resin may be incorporated in the grinding vehicle when the paste is milled or it may be incorporated in the thinning vehicle when the milled paste is thinned. It has been found that the optimum amount of nondrying or essentially nondrying alkyd resin is between about %-30% by weight of the total vehicle. Amounts less than about 10% by Weight, while giving sporadic improvements in film flexibility, do not yield consistently good results. Amounts greater than about 30% by weight of total vehicle tend to unreasonably extend the cure time and to cause bloom on the surface of the final cured film. The remaining ingredients in the paint are selected according to standard practice.

As pigments, there may be used such materials as lithopone, titanium dioxide, titanium calcium pigment, and zinc oxide. Coloring matter, such as lead chromate pigment, may be used where color is desired. Fillers, such as whiting, barytes, print clay, and blame fixe, are preferably also included as part of the paint composition. An antioxidant such as that obtained from the destructive distillation of lignin and sold under the name Guaiaphene is also preferably included. The usual driers may be added to the composition. A typical paste formulation is shown below:

Pigment 28 Filler 51 Vehicle 20 Antioxidant 0.6 Composite drier 0.4

The pigments are dispersed in the grinding vehicle by means of a three-roll mill. The above vehicle is known as the grinding vehicle and its viscosity should preferably not exceed approximately W on the Gardner-Holdt scale. Organic solvents, either aliphatic or aromatic or mixtures thereof, may be used to control the viscosity for good grinding in accordance with known methods. In the practice of the present invention, the nondrying alkyd resin may be substituted in the grinding vehicle; slightly improved results are obtained in this manner.

To 100 parts of the paste prepared as described above there is normally added 29 parts of thinning vehicle and 1 part of a flow control agent, usually a heavy-bodied, heavily leaded linseed oil. In the practice of the present invention, the nondrying alkyd resin may be added to the paint composition in the thinning vehicle if desired. Alternatively, the total amount of nondrying alkyd resin to be added may be split between the grinding vehicle and the thinning vehicle.

Once the thinning Vehicle has been added, the paint may then be thinned with a solvent such as mineral spirits until good leveling is secured. The ratios of vehicle solids in the above-described paint composition are 20 (grinding vehicle) :29 (thinning vehicle):l (flow control). All the vehicles consist of the vinyl toluene modified siccative oil, and the amount of nondrying or essentially nondrying alkyd resin to be added is based on the total vehicle, both grinding and thinning.

The following examples illustrate several modifications of the invention. All parts are by weight unless otherwise stated.

Example 1 A regular white paste was made according to the following typical formulation:

Pigment 28 Filler 51 Vehicle (vinyl toluene modified linseed oil) 20 Antioxidant 0.6 Drier 0.4

The vehicle used in the paste described above had an oil length of 40%, a solids content of 70%, and a viscosity of Z-2 to Z3.

The pastes were ground on a three-roll mill and then were thinned as follow:

Paste Vehicle (same as grinding vehicle) 29 Flow control agent 0.5 Solvent 1530 A nondrying tallow-pentaerythritol-phthalic anhydride alkyd was incorporated into the vehicle during thinning. The nondrying alkyd had an oil length of 65% and a solids content of 100%. The nondrying alkyd was used to replace varying amounts of the thinning vehicle; the quantities employed were calculated on the basis of the entire vehicle in the paint, e. g., the total vehicle in an amount of 50 parts.

The following paint formulations were prepared:

Percent Modiflcatlon 0 3.1% 5.9% i 8.9%

Paste 109 109 109 109 Thinning vehicle (70% solids) 41 39. 4 37. 3 35. 2 Flow contr 0. 5 0. 5 0. 5 0.5 Tallow alkyd- 1. 5 2. 9 4. 4 Solvent, mL. 13 16 14 17 It can be seen from the above that replacement of the vinyl toluene modified siccative oil with a nondrying alkyd yields maturing rates about equivalent to the control but not as satisfactory as with 0 replacement; the higher the maturing values, the better the cure.

The following tensile strength and elongation data were obtained:

The tensile strength and elongation data listed above show that partial replacement of the usual vinyl toluene modified siccative oil alkyd with small amounts of nondrying alkyd yields small improvements in flexibility. These improvements do not measure up to the control. The data indicate, however, that increasing the amount of replacement gives increasing flexibility.

Example 11 A paint formulation was prepared wherein the vinyl toluene modified siccative oil was replaced to the extent of 18% by the nondrying alkyd used in Example I. The following is the formulation:

18% modification Paste 109 Thinning vehicle (70% solids) 28.6 Flow control 0.5 Tallow alkyd 9.0 Solvent, ml 18 Example III Paints were prepared wherein the vinyl toluene modified siccative oil had a working viscosity at 64% solids. The nondrying alkyd was a coconut oil-pentaerythritolphthalic anhydride resin and was based on 65% coconut oil length and was employed at 89% solids. The following paint formulations were prepared:

Percent Modification 30 Paste 111 111 Thinning vehicle (64%)." 45. 3 22 Flow control 1. 0 0. 5 Coconut alkyd (89%) 8. 5

This concentration of nondrying alkyd was too high, since the solvent tolerance of the paint was reduced and gloss impaired. The surface appearance was improved, but surface tackiness was observed. At 21% modification, however, an excellent paint resulted. The following curing data have been obtained:

Maturing 3 days at 165 F. Control 32 0% replacement 21 21 replacement 35 30 replacement 8 The following tensile strength and elongation data are obtained:

Tensile Strength and Elongation Data Cure Time 3 Days at 165 F.

1 Month 3 Months Percent T. S. E.

T. S. Percent T. S. Percent Control 98 22 114 22 108 16 0% replacement. 105 8 100 6 87 3 21% replacement 92 21 101 24 101 19 30% replacement". 50 23 55 26 58 15 We claim:

1. A paint composition according to claim 3 wherein said nondrying glyceride oil comprises beef tallow.

2. A paint composition according to claim 3 wherein said nondrying glyceride oil comprises coconut oil.

3. A paint composition comprising filler, pigment, solvent, and a vehicle comprising about %70% by weight vinyl toluene-siccative oil coplymer, and about 10%30% by weight nondrying alkyd resin comprising the reaction product of about 40-90% by weight of a nondrying glyceride oil with a polyhydric alcohol and an aromatic dibasic acid, wherein the hydroxyl equivalents of said alcohol are in 10-30% excess of the carboxyl equivalents of said acid.

4. A paint composition according to claim 3 wherein said siccative oil comprises linseed oil.

5. A paint composition comprising filler, pigment, solvent, and a vehicle comprising about 90%-70% by weight vinyl toluene-linseed oil copolymer and about 10%-30% by weight nondrying alkyd resin comprising the reaction product of about 4090% by weight of a nondrying glyceride oil with pentaerythritol and phthalic anhydride, wherein the hydroxyl equivalents of said pentaerythritol are in 10-30% excess of the carboxyl equivalents of said phthalic anhydride.

6. A paint composition according to claim 5, wherein said nondrying glyceride oil comprises beef tallow.

7. A paint composition according to claim 5 wherein said nondrying glyceride oil comprises coconut oil.

Vermorken: Vinyltoluene, La Chemie des Peintures, volume 17, pages 238-243 (1954). (Copy in Scientific Library.)

Claims (1)

1. 3. A PAINT COMPOSITION COMPRISING FILLER, PIGMENT, SOLVENT, AND A VEHICLE COMPRISING ABOUT 90%-70% BY WEIGHT VINYL TOLUENE-SICCATIVE OIL COPOLYMER, AND ABOUT 10%-30% BY WEIGHT NONDRYING ALKYD RESIN COMPRISING THE REACTION PRODUCT OF ABOUT 40-90% BY WEIGHT OF A NONDRYING GLYCERIDE OIL WITH A POLYHYDRIC ALCOHOL AND AN AROMATIC DIBASIC ACID, WHEREIN THE HYDROXYL EQUIVALENTS OF SAID ALCOHOL ARE IN 10-30% EXCESS OF THE CARBOXYL EQUIVALENTS OF SAID ACID.