# Patent

## Title
Resin for magnetic paint

## Abstract

Disclosed is an improved plastisol composition comprising a finely-divided vinyl chloride polymer, filler, a primary plasticizer, and a polyaminoamide-polyimidazoline adhesion promoter. The improvement for overcoating said plastisol with an acid catalyzed topcoat comprises a plasticizer/promoter phase which comprises said primary plasticizer, said adhesion promoter, and an effective amount of a secondary plasticizer non-ionic solvent effective in solvating the adhesion promoter in the plasticizer/promoter phase. The plasticizer/promoter phase is pre-formed for addition with the remaining ingredient for the plastisol composition.

## Background
The present invention relates to plastisols in general and in particular to improved adhesion promter systems for polyvinyl chloride (PVC) plastisols.

Vinyl chloride homopolymers (PVC) and copolymers are widely used for the protection of metallic surfaces against corrosion, for adhering thin sheet metal constructions, and for sealiing welded seams, particularly in the automotive industry. Such coatings principally are applied in the form of plasticized vinyl chloride polymers (plastisols) by a variety of techniques. Depending upon the viscosity of the PVC plastisol, its utilization can be characterized as a sealant, caulk, coating, adhesive, or other function.

Since resistance to corrosion is a prime prerequisite in dealing with metal parts, the PVC plastisol should adhere to the metal part with a fair degree of tenacity; otherwise, oxidation undercutting would result. Despite the ability to control the texture of the plastisol by suitable fillers and the color by the addition of suitable tinctorial pigments, often the PVC plastisol must be overcoated with a high performance, e.g. acrylic, topcoat, especially in automotive uses of the PVC plastisol. Uniformity in visual appearance dictates such overcoating requirement typically.

Another requirement of the PVC plastisol is that it be curable at short, low bake cycles. In fact, successful plastisols and organisols in the automotive industry are being called on today to be curable, dry to the touch, at baking temperatures of less than 300.degree., e.g. about 275.degree. F., with oven residence times of about 20-30 minutes. Energy costs dictate such low temperature, short baking cycles. Further, successful plastisol and organisol formulations must be economic and expel a minimum of atmospheric pollutants.

While a variety of adhesion promoters have been proposed for PVC plastisols and organisols, most have suffered from a variety of drawbacks including cost, insufficient film flexibility, or the like. One class of adhesion promoters which appears to exhibit a good balance between cost, flexibility, and low temperature bake characteristics are polyaminoamide-polyimidazoline adhesion promoters such as set forth in U.S. Pat. No. 4,146,520. Such adhesion promoters have enabled the formulation of advantageous PVC plastisols and organisols which can be baked at temperatures as low as about 250.degree. F. Unfortunately, the plastisols and organisols containing such polyaminoamide-polyimidazoline adhesion promoters are not readily overcoated with acid-catalyzed topcoats, especially high performance acid catalyzed acrylic automobile finishes. It is theorized that the amine value of the adhesion promoters interacts and renders ineffectual the acid catalyst in the topcoat, thus resulting in tacky films. While reduction of the level of the adhesion promoter can overcome such topcoat tackiness, loss of adhesion also can occur at such low adhesion promoter levers. Thus, there is a need in the art to enable the utilization of polyaminoamide-polyimidazoline adhesion promoters in low bake PVC plastisol and organisol compositions, yet provide the ability to overcoat such plastisols with acid catalyzed topcoats.

The present invention is addressed to the need in the art to retain advantageous low bake properties of PVC plastisols and their requisite good adhesion to metal, yet still be able to be coated wet-on-dry or wet-on-wet by acid catalyzed topcoats. Accordingly, the present invention is directed to plastisol compositions comprising finely-divided vinyl chloride polymer, filler, a primary plasticizer, and a polyaminoamide-polyimidazoline adhesion promoter. The improvement of the present invention comprises a plasticizer/promoter phase comprising said primary plasticizer, said adhesion promoter, and an effective amount of a secondary plasticizer nonionic solvent effective in solvating said adhesion promoter in said plasticizer/promoter phase wherein the plasticizer/promoter phase is preformed for addition with the remaining ingredients of the plastisol composition. Suitable nonionic secondary plasticizer solvents include aromatic solvents and polyalkylene glycol ether solvents which are effective in solvating the polyaminoamide-polyimidazoline adhesion promoters.

Another aspect of the present invention involves the method for formulating the improved plastisol compositions wherein the plasticizer/promoter phase comprising the primary plasticizer, the adhesion promoter, and the secondary plasticizer nonionic solvent is pre-formed and than such phase added to the remaining ingredients of the plastisol composition.

Advantages of the present invention include the retention of low bake characteristics of the plastisol and the excellent adhesion characteristics of the plastisol. A further advantage is the ability to overcoat the plastisol wet-on-dry or wet-on-wet with an acid catalyzed topcoat (i.e. "paintability", for present purposes) which is dry to the touch at lower bake temperatures of about 250.degree.-360.degree. F., for example. A further advantage is the ability to exhibit the foregoing advantageous characteristics while retaining the flexibility of controlling the rheological characteristics of the plastisol. A further advantage is an improved plastisol composition which exhibits excellent controlled age characteristics. These and other advantages will be readily apparent to those skilled in the art based upon the disclosure contained herein.

The polyaminoamide-polyimidazoline adhesion promoters are set forth in U.S. Pat. No. 4,146,520. Such adhesion promoters include condensation products formed between a polymerized fatty acid mixture and an excess of polyalkylene polyamine. Such adhesion promoters additionally include the foregoing condensation product further reacted with an aldehyde, a ketone, or an epoxy compound.

While not intending to be bound by theory, it appears that a significant quantity of the adhesion promoter migrates to the surface of the cured plastisol. While such migration does not adversely impact the performance of the plastisol, it does adversely affect the curability of acid catalyzed topcoats which then are applied to the wet (wet-on-wet) or dry (i.e. wet-on-dry) plastisol. It is believed that the amine value of the adhesion promoter reacts with the acid catalyst in the topcoat which means that the topcoat will not be fully cured at the recommended bake temperatures of about 300.degree. F. or thereabouts. As noted above, such undesirable interaction can be mostly obviated by a reduction of the amount of adhesion promoter in the plastisol, though such reduction compromises the degree of adhesion achievable, so that this alternative is not commercially viable. The same holds true for increasing the amount of acid catalyst in the acid catalyzed topcoat.

One way of viewing the result of the invention is that the adhesion promoter is rendered more compatible or homogeneous in the plastisol so that it does not overconcentrate at the film surface. Accordingly, appropriate secondary plasticizer solvents or diluents should be effective in solvating the polyaminoamide-polyimidazoline adhesion promoters. Next, such secondary plasticizer solvents should be non-ionic. Solvents rich in amine value, for example, should be avoded even though they may effectively solvate the adhesion promoters as such solvents only contribute to the problem being solved. Accordingly, nonionic solvents are recommended.

Suitable nonionic solvents which solvate the adhesion promoter include aromatic solvents and polyalkylene glycol ether solvents. By "solvate", we mean that a clear, stable solution results upon the mixing of the nonionic solvent and the adhesion promoter, typically at room temperature though moderate heating may be employed. Suitable such nonionic solvents include, for example, monoisopropyl biphenyl, diethylene glycol monoethyl ether, diisopropyl biphenyl, phenylxyleyl ethane, butylated biphenyl, and the like and mixtures thereof. The proportion of the secondary plasticizer solvent is adjusted to accomplish its function in the formulation. Often, this means between about 10 and 70 phr nonionic solvent is used.

The remaining ingredients in the plastisol are conventional and include finely-divided polyvinyl chloride homopolymers on vinyl chloride copolymers, and often blends thereof. The primary plasticizer most often will be an alkyl phthalate such as dihexyl phthalate, diisodecyl phthalate, and the like. Alternatively, the primary plasticizer may be an alkyl adipate (e.g. di(2-ethyl hexyl)adipate) or the like. The plasticizer typically will range from about 20 to 200 phr (weight parts per 100 weight parts of PVC resin).

Additionally the plastisol will contain a filler for control of rheology, control of cost, and the like. Suitable fillers include, for example, calcium carbonate, glass (including hollow glass spheres), talc, chalk, barium sulfate, and the like. The fillers certainly affect paintability of the plastisol, though with the invention more flexibility in filler utilization is gained. The proportion of filler can range up to about 300 phr and the optimum will vary depending upon the type of PVC and plasticizer, and the rheology desired. Finally, thixotropic agents can be added to achieve certain plastisol rheologies and such agents include, for example, fumed silica, bentonite, metallic fatty acid soaps, and the like. Thixotropic agents typically are added in the range of about 1-5 phr.

In order to maximize the paintability of the plastisol (i.e. ability to coat the plastisol with an acid catalyzed topcoat), it has been determined that a pre-blend of adhesion promoter, primary plasticizer, and nonionic secondary plasticizer solvent should be made. Such plasticizer/promoter blend is added to the remaining ingredients for forming the plastisol. Apparently, the formation of the plasticizer/plastisol blend is more effective in compatibilizing the adhesion promoter in the plastisol or "pushing" the plasticizer into the PVC particles. Regardless of the mechanism involved, it has been determined that paintability of plastisol becomes a routine achievement when the plasticizer/promoter blend is initially formed in making the plastisol composition.

The plastisol is dryable or curable at very low bake temperatures ranging on down to about 250.degree.-275.degree. F. The plastisol either can be baked and then topcoated (wet-on-dry) or the plastisol can be applied followed by the topcoat wherein both coatings then are cured in a single bake (wet-on-wet). In automotive applications, the plastisol typically is drawn down or applied onto a metal subsrate which has been primed with a corrosion-inhibiting coating. Typical topcoats include high performance acrylic topcoats which are cured by conventional acid catalysts.

The following examples show how the present invention has been practiced but should not be construed as limiting. All percentages and proportions are by weight unless expressly indicated. Also, all citations disclosed herein are incorporated expressly herein by reference.

The efficacy of polyaminoamide-polyimidazoline adhesion promoters in PVC plastisol formulations was demonstrated on the following general formulation. ______________________________________ Ingredient*        Amount (wt.-parts) ______________________________________ occidental 6482    60 Borden VC265       40 Dihexyl phthlate (DHP) 62.5 Diisodecyl phthlate (DIDP) 62.5 CaCO.sub.3         250 ______________________________________ *Occidental 6482A medium molecular weight PVC homopolymer, inherent viscosity 1.07 (ASTM D1243), K Value (Fikenstscher) 71, specific gravity 1.414 (ASTM D792), gelatin temperature 163.degree. F., 100% passes throug a 325 mesh sieve, Occidental Chemical Corp., Pottstown, Pa. Borden VC265PVC copolymer plastisol blending resin containing 4% vinyl acetate, 3340 micron avg. particle size powder, Borden, Inc., Columbus, Oho. CaCO.sub.3 --Atomite brand CaCO.sub.3, 3 micron mean particle size, Thompson, Weineman, and Company, Cartersville, Georgia.

Varying levels of adhesion promoter were utilized as follows: ______________________________________ Formulation No.  Wt. Parts ______________________________________ 204-65-1         10.17 204-65-2         7.13 204-65-3         4.75 204-65-4         3.56 204-65-5         2.38 204-65-6         1.19 204-65-7         0.59 ______________________________________

The adhesion promoter was Euretek 580 polyaminoamide adhesion promoter (amine value of 190, manufactured under U.S. Pat. No. 4,146,520, Sherex Chemical Company, Inc., Dublin, Ohio).

Brookfield viscosity measurements were taken on each formulation initially and thereafter at various intervals of time. The following data was recorded. __________________________________________________________________________ Viscosity (cps) No. RPM Initial 3 days 7 days 17 days 24 days 32 days 45 days __________________________________________________________________________ 1  2.5 154,800 267,200 350,400 334,400 348,800 339,200 324,800 5   99,400 184,800 249,600 254,400 255,200 244,800 232,800 10  66,600 125,600 174,800 177,200 178,800 176,400 165,600 20  47,350 91,800 129,000 130,600 133,000 134,600 125,600 R   3.27 2.91 2.72 2.56 2.62 2.52 2.59 yield 2,770 4,120 5,040 4,000 4,680 4,720 4,500 2  2.5 143,200 283,200 302,400 304,000 272,000 267,200 275,200 5   91,600 188,800 199,200 209,600 175,200 177,600 185,600 10  59,300 122,800 130,000 138,800 117,600 119,600 124,800 20  40,800 85,600 90,800 97,400 84,800 87,200 90,800 R   3.58 3.31 3.33 3.12 3.21 3.06 3.03 yield 2,580 4,720 5,160 4,720 4,840 4,480 4,480 3  2.5 214,400 276,800 312,000 313,600 324,800 262,400 244,800 5   137,600 171,200 192,800 197,600 205,600 164,800 152,800 10  87,200 106,400 120,400 126,400 134,800 105,600 98,400 20  57,200 69,200 78,000 85,800 93,800 72,600 65,400 R   3.75 4.00 4.00 3.66 3.46 4.47 3.74 yield 3,840 5,280 5,960 5,800 5,960 4,880 4,600 4  2.5 228,800 320,000 342,400 328,000 307,200 276,800 5   147,200 200,800 212,800 203,200 189,600 168,800 173,600 10  93,600 124,800 133,200 127,600 118,400 105,600 109,680 20  61,200 80,600 88,400 83,600 78,400 70,200 73,600 R   3.74 3.97 3.87 3.92 3.92 3.85 1.59 yield 4,080 5,960 6,480 6,240 5,880 5,080 5,000 5  2.5 275,200 347,200 315,200 328,000 310,400 289,600 276,800 5   177,600 216,800 189,600 202,400 192,000 178,400 173,600 10  113,200 134,000 114,000 124,800 119,200 109,600 109,200 20  73,200 85,800 73,600 80,400 76,800 71,400 72,800 R   3.76 4.05 4.28 4.08 4.04 4.06 3.80 yield 4,880 6,520 6,280 6,280 5,920 5,560 5,160 6  2.5 345,600 398,400 361,600 342,400 360,000 342,400 318,400 5   245,600 246,400 224,000 208,800 218,400 209,600 197,600 10  158,400 150,800 136,400 127,200 131,600 126,800 120,800 20  99,800 93.600 84,800 78,800 82,200 78,800 75,600 R   3.46 4.26 4.26 4.35 4.38 4.35 4.21 yield 5,000 7,600 6,880 6,880 7,080 6,640 6,040 7  2.5 387,200 449,600 420,700 424,000 414,400 392,000 395,200 5   274,400 276,800 250,400 253,600 247,200 231,200 235,200 10  171,200 165,200 147,200 150,400 146,800 137,200 140,000 20  104,800 98,800 90,000 91,400 88,800 82,600 86,200 R   3.69 4.55 4.68 4.64 4.67 4.75 4.58 yield 5,640 8,640 8,520 8,520 8,360 8,040 8,000 __________________________________________________________________________ *Spindle #6 for 20465-1 and 2, and Spindle #7 for all other samples. R is a measure of the degree of thixotropy and is calculated by dividing the viscosity at 2.5 rpm by the viscosity at 20 rpm. Yield is a measure of the force required to move the plastisol (thickness of the plastisol) and is calculated as follows: ##STR1##

Advantageously, the viscosity should stabilize over time. The above-tabulated data demonstrates such viscosity stability.

Each formulation was drawn down (0.020 inch coating) on primed steel panels (Uni-Prime coated panels, PPG Industries, used in all examples) and baked for 20 minutes at 121.degree. C. Each coating had good adhesion to the panels except for 204-65-7, indicating that the promoter level was too low.

The coated panels then were coated with a white enamel paint (an automotive topcoate based on melamine and a hydroxyl-acrylic resin with an acid catalyst, supplied by PPG Industries, Pittsburgh, Pa.) The topcoated panels were baked at 121.degree. C. for 30 minutes. All samples were slightly tacky and eventually intercoat adhesion was lost (about 50 days). This demonstrates the difficulties encountered in curing an acid catalyzed topcoat over a primer high in amine value. Thus, while metal adhesion and controlled age viscosity were good, paintability was lacking.

Plasticizer studies extended to various blends in order to retain control age viscosity but improve paintability. The basic formulation studied was as follows: ______________________________________ Ingredient*     Amount (wt.-parts) ______________________________________ Occidental 6482 60 Borden VC265    40 CaCO.sub.3      100 Talc            20 Silica          1 Euretek 580 promoter 3.21phr ______________________________________ Talc  Mistron ZCS grade talc, Cypress Industrial Minerals Silica  CabO-Sil brand fumed silica, Cabot Corporation. Promoter  phr is weight parts per hundred weight parts of PVC.

The various plasticizer/promoter phases evaluated are set forth below: ______________________________________ Formulation No. 204-88 (wt.-parts) Ingredient 1     2        3   4      5   6 ______________________________________ DIHP       50    50       50  50     50  50 DHP        10    20       25  50     50  100 Monoiso-   40    30       25  --     --  40 propyl biphenyl ______________________________________

In formulations 1-3 and 5, the promoter was added to the plasticizer mix slightly warmed until homogeneous. In formulations 4 and 6, the promoter was added after the plastisol was made. Age viscosity measurements were taken as set forth below. ______________________________________ Viscosity (cps) No.  RPM     Initial 1 day 4 days 11 days 22 days 34 days ______________________________________ 1    2.5     217,600 188,800 273,600 236,800 251,200 244,800 5       128,800 113,600 179,200 154,400 172,000 174,400 10      79,600  69,600 111,600 101,200 119,600 118,800 20      50,800  46,800 74,400 69,000 84,200 85,800 R       4.28    4.03  3.68  3.43  2.98  2.85 yield   4,440   3,760 4,720 4,120 3,960 3,520 2    2.5     224,000 212,800 212,400 300,800 304,000 308,800 5       132,800 126,400 165,600 201,600 212,000 211,200 10      80,800  77,600 105,200 141,600 150,400 148,800 20      50,800  49,400 69,600 103,400 115,800 117,400 R       4.41    4.31  3.77  2.91  2.63  2.63 yield   4,560   4,320 4,840 4,960 4,600 4,880 3    2.5     220,800 192,000 241,600 246,400 275,200 275,200 5       122,400 115,200 148,000 153,600 172,800 180,800 10      73,200  70,400 93,600 97,200 113,200 25,200 20      46,000  45,600 63,600 65,600 77,200 88,800 R       4.80    4.21  3.80  3.76  3.56  3.10 yield   4,920   3,840 4,680 4,640 5,120 4.720 4    2.5     217,600 214,400 227,200 235,200 233,600 246,400 5       131,200 128,800 139,200 140,800 139,200 150,400 10      81,600  79,600 85,600 86,000 86,800 95,200 20      51,400  50,800 54,600 56,200 56,400 63,400 R       4.23    4.22  4.16  4.19  4.14  3.89 yield   4,320   4,280 4,400 4.720 4,720 4,800 5    2.5     230,400 204,800 214,400 212,800 217,600 217,600 5       139,200/ 125,600 130,400 128,800 131,200 132,800 10      85,600  78,400 81,600 79,200 81,600 82,400 20      53,800  50,800 52,600 51,200 51,600 53,400 R       4.28    4.03  4.08  4.16  4.22  4.07 yield   4,560   4,960 4,200 4,200 4,320 4,240 6    2.5     193,600 204,800 225,600 196,800 249,600 254,400 5       124,800 128,800 138,400 122,400 156,800 161,600 10      75,200  78,400 84,600 74,800 08,000 109,600 20      46,200  50,000 54,600 51,600 64,800 70,600 R       4.19    4.09  4.13  3.81  3.85  3.32 yield   3,440   3,800 4,360 3,720 4,640 4,640 ______________________________________ Spindle # 7 for all samples.

Coatings on primed steel panels (0.020 inch thickness) were baked at 121.degree. C. for 20 minutes. All films adhered well except No. 204-88-5 (control). The acid catalyst topcoat of Example 1 was applied over the cured plastisols and baked at 121.degree. C. for 30 minutes (wet-on-dry). Nos. 1-3 were dry while Nos. 4 and 5 were slightly tacky. Thus, the paintability of the plastisol had been improved by the addition of the secondary plasticizer solvent, monoisopropyl biphenyl. The amount of secondary plasticizer solvent appeared to be a bit low in Nos. 2 and 3, so that the formulation of this example appears to require at least about 40 weight parts of monoisopropyl biphenyl in order for paintability to be realized.

The basic formulation of Example 2 (Table 4) was studied again at higher levels of monoisopropyl biphenyl: 50 wt.-parts for 204-96-1 and 70 wt.-parts for 204-96-2. Again, the technique of blending the adhesion promoter into the plasticizer blend prior to making the plastisol was utilized. The age viscosity data recorded is set forth below. __________________________________________________________________________ Viscosity (cps) No. RPM Initial 1 day 6 days 14 days 21 days 30 days 45 days __________________________________________________________________________ 1  2.5 142,000 161,600 172,000 174,400 815,600 195,200 180,000 5   86,600 99,200 106,400 115,200 120,800 126,400 111,400 10  55,100 62,900 67,800 74,400 78,800 84,000 71,700 20  36,350 41,650 46,200 48,200 52,800 56,600 47,100 R   3.91 3.88 3.72 3.62 3.52 3.45 3.77 yield 2,770 3,120 3,280 2,960 3,240 3,440 3,430 2  2.5 174,400 118,400 105,600 124,800 134,400 140,800 163,200 5   115,600 105,600 98,400 101,600 104,400 123,200 122,400 10  74,700 88,400 90,400 96,400 98,800 99,200 101,600 20  48,300 64,800 69,200 79,200 81,600 77,400 82,400 R   3.61 1.83 1.33 1.58 1.65 1.82 1.98 yield 2,940 640 360 1,160 1,000 880 2,040 __________________________________________________________________________ Spindle # 6 for Initial, 1 day, and 6 days for No. 1 and for Initial for No. 2; Spindle # 7 for all other samples.

Each plastisol exhibited good adhesion to the steel panels (bake protocol of 121.degree. C. for 20 minutes). The acid catalyzed topcoat of Example 1 was applied wet-on-dry and wet-on-wet with baking at 121.degree. C. for 30 minutes for both. The topcoat was not tacky for both systems. Note the slightly increased secondary solvent levels used compared to Example 2. Thus, the ability to achieve paintability while retaining adhesion to metal has been achieved.

The following formulations were studied. ______________________________________ Formulation No. 204-147 (wt-parts) Ingredient           1      2 ______________________________________ Occidental 6482      60     60 Borden VC265         40     40 CaCO.sub.3           200    200 Talc                 10     10 DIDP                 60     60 Monoisopropyl biphenyl 40     40 Euretek 580 promoter 3      3 ______________________________________

The plasticizer/promoter blend of No. 1 was mixed at room temperature and then added to the plastisol. The plasticizer/promoter blend of No. 2 was mixed at 72.degree. C. and then added to the plastisol. The effects of temperature during the formulating, thus, were being studied.

Both plastisols were coated on steel panels and subjected to wet-on-dry and wet-on-wet topcoating as in Example 3. No apparent performance difference between the two formulations observed.

Various secondary plasticizer solvents were studied utilizing the basic formulation of Example 2. The various plasticizer blends studied are set forth below: ______________________________________ Formulation No. 204-98 (wt-parts) Ingredient      1                3 ______________________________________ DIDP            50         50    50 DHP             10         10    10 Butylated biphenyl 40         --    -- Diisopropyl biphenyl --         40    -- Phenylxyleyl ethane --         --    40 ______________________________________

The plasticizer/promoter blends were made and then added to the remaining ingredients, as described above. Age viscosity data are set forth below. ______________________________________ Viscosity (cps) No.   RPM     Initial  6 days 14 days 30 days 45 days ______________________________________ 1     2.5     212,800  198,400 190,400 201,600 185,600 5       147,200  120,800 113,600 121,600 111,200 10      96,000   74,800 70,400 75,600 69,600 20      62,400   48,200 45,400 50,600 45,000 R       3.41     4.12  4.19   3.98  4.12 yield   3,280    3,880 3,840  4,000 3,720 2     2.5     259,200  225,600 206,400 214,400 206,400 5       172,000  136,800 124,800 131,200 123,200 10      106,800  84,800 76,400 82,000 77,200 20      68,200   54,400 50,600 55,400 50,800 R       3.80     4.15  4.08   3.87  4.06 yield   4,360    4,440 4,080  4,160 4,160 3     2.5     171,200  195,200 195,200 188,800 190,400 5       143,200  125,600 120,800 117,600 121,600 10      98,800   78,000 75,600 71,200 74,800 20      64,000   51,600 50,800 47,200 49,600 R       2.68     3.78  3.84   4.00  3.84 yield   1,400    3.480 3,720  3,560 3,440 ______________________________________ Spindle # 7 for all samples.

The formulations were coated and cured on steel panels (121.degree. C. for 20 minutes) and topcoated wet-on-dry and wet-on-wet as in the previous examples. Again, good adhesion to the substrates was achieved. The wet-on-dry topcoats also were tack free while the wet-on-wet topcoats were very slightly tacky. Thus, the efficacy of additional aromatic secondary plasticizer solvents is demonstrated.

The following formulations were made as described above. ______________________________________ Formulation no.204-116 (wt.-parts) Ingredient       1      2        3    4 ______________________________________ Occidental 6482  60     60       60   60 Borden VC265     40     40       40   40 CaCO.sub.3       200    200      200  200 DIDP             60     60       60   30 DHP              --     --       --   30 Euretek 580 promoter 5      3        3    3 Monoisopropyl biphenyl 40     40       --   -- Diethylene glycol --     --       40   40 monoethyl ether ______________________________________

Control age viscosity data recorded is set forth below. ______________________________________ Viscosity (cps) No.   RPM     Initial  3 days 14 days 25 days 31 days ______________________________________ 1     2.5     211,200  206,400 233,600 241,600 284,800 5       171,200  196,800 220,800 215,200 237,600 10      115,200  153,200 175,600 164,400 180,800 20      79,600   106,600 126,400 121,600 137,600 R       2.65     1.94  1.85   1.99  2.07 yield   2,000    480   640    1,320 2,360 2     2.5     219,200  256,000 262,400 278,400 281,600 5       144,000  211,200 228,800 246,400 231,200 10      98,400   153,600 169,200 180,000 172,400 20      60,600   109,400 115,400 132,400 124,200 R       3.62     2.34  2.27   2.10  2.27 yield   3,760    2,240 1,680  1,600 2,520 3     2.5     6,240    15,520 33,200 33,200 34,400 5       5,040    12,080 23,200 25,000 25,600 10      4,320    9,760 17,800 20,400 20,500 20      3,860    8,120 14,600 16,550 16,750 R       1.62     1.91  2.27   2.00  2.05 yield   60       172   500    410   440 4     2.5     5,440    15,360 32,800 40,400 44,800 5       4,480    12,240 25,000 31,400 34,800 10      3,840    10,160 20,200 25,600 28,100 30      3,340    8,920 17,050 21,950 23,850 R       1.63     1.72  1.92   1.84  1.88 yield   48       156   390    450   500 ______________________________________ Spindle # 7 for No. 1 and No. 2; Spindle # 5 for Initial and 3 days for No. 3 and No. 4; Spindle # 6 for remaining samples.

The plastisols were coated on panels (121.degree. C. for 20 minutes) and topcoated wet-on-dry as described in the previous examples. Again, good substrate adhesion was achieved. The topcoats were dry for Nos. 2, 3, and 4, and only very slightly tacky for No. 1. Again, the low temperature paintability of the inventive plastisols is demonstrated.

Additional studies of the ether secondary plasticizer solvent were undertaken on the following formulations. ______________________________________ Formulation No. 204-98 (wt.-parts) Ingredient      1          2      3 Occidental 6482 60         60     60 Borden VC265    40         40     40 CaCO.sub.3      200        200    200 DIDP            90         80     105 Diethylene glycol 10         20     20 monoethyl ether Euretek 580 promoter 3          3      3 ______________________________________

Control age viscosity data is set forth below. ______________________________________ Viscosity (cps) No.  RPM     Initial 1 day 3 days 10 days 21 days 24 days ______________________________________ 1    2.5     128,800 170,400 249,600 283,200 267,200 254,400 5       78,600  104,000 151,200 177,600 167,200 158,400 10      50,200  66,400 96,400 114,400 108,400 102,400 20      33,950  44,900 63,200 79,200 74,800 70,800 R       3.79    3.80  3.95  3.58  3.57  3.59 yield   2,510   3,320 4,920 5,280 5,000 4,800 2    2.5     65,600  98,400 135,200 161,200 170,800 164,800 5       40,200  59,400 82,400 96,800 106,600 100,200 10      25,600  38,200 52,600 63,800 69,700 64,900 20      17,700  25,800 36,000 45,050 47,350 44,950 R       3.71    3.82  3.76  3.58  3.61  3.67 yield   1,270   1,950 2,640 3,220 3,210 3,230 3    2.5     35,680  59,520 82,720 109,600 105,600 101,200 5       20,880  35,360 48,960 65,200 63,600 60,400 10      18,000  22,080 30,240 40,300 39,600 37,300 20      8,620   14,500 19,600 26,300 26,200 24,600 R       4.14    4.10  4.22  4.17  4.03  4.11 yield   740     1,208 1,688 2,220 2,100 2,040 ______________________________________ Spindle # 6 for No. 1 and No. 2; Spindle # 5 for No. 3.

Good adhesion to steel panels again was achieved. The wet-on-dry topcoats (121.degree. C. for 30 minutes) also were dry. The efficacy of the ether secondary plasticizer solvent again is demonstrated.

Formulation No. 204-118-1 (Example 7) was evaluated again along with an equivalent formulation which used a different adhesion promoter (No. 2) at the same level: Euretek 555 polyaminoamide-polyimidazoline adhesion promoter (amine value of 380; Gardner color of 12; 8.1 lb/gal. at 82.2.degree. C.; Viscosity profile (Brookfield LVT, spindle 34) of 17,000 cps at 43.3.degree. C., 13,000 cps at 48.9.degree. C., 9,000 cps at 54.5.degree. C., 4,000 cps at 60.0.degree. C., and 2,800 cps at 65.6.degree. C.; Sherex Chemical Company, Inc., Dublin, Ohio). The control age viscosity data recorded is set forth below. ______________________________________ Viscosity (cps) No.  RPM     Initial 1 day 3 days 10 days 21 days 24 days ______________________________________ 1    2.5     128,800 170,400 249,600 283,200 267,200 254,400 5       78,600  104,000 151,200 177,600 167,200 158,400 10      50,200  66,400 96,400 114,400 108,400 102,400 20      33,950  44,900 63,200 79,200 74,800 70,800 R       3.79    3.80  3.95  3.58  3.57  3.59 yield   2,510   3,320 4,920 5,280 5,000 4,800 2    2.5     130,800 145,600 185,600 154,800 154,800 5       82,000  87,800 93,600 94,600 95,800 10      52,700  55,700 59,800 61,400 62,600 20      35,650  37,900 41,950 42,600 43,800 ______________________________________ See Example 7 for No. 1; Spindle # 6 for No. 2.

Panel coatings and wet-on-dry acid catalyzed topcoats were applied as in the previous examples. Good panel adhesion was achieved. The topcoat on Formulation No. 204-118-1 was dry while the topcoat on Formulation No. 204-126-2 was only slightly tacky.

The following formulations were made: ______________________________________ Formulation No. 204-120 (wt.-parts) Ingredient      1          2      3 ______________________________________ Occidental 6482 60         60     60 Borden VC265    40         40     40 CaCO.sub.3      200        200    200 DIDP            90         80     55 Diethylene glycol 10         20     20 monoethylene ether Euretek 580 promoter 3          3      3 ______________________________________

Control age viscosity data is set forth below. ______________________________________ Viscosity (cps) No.     RPM     Initial  1 day  10 days 21 days ______________________________________ 1       2.5     108,800  158,400 334,400 318,400 5       66,600   96,800 212,800 203,200 10      43,300   61,600 137,600 131,200 20      30,000   41,600 92,800 90,800 R       3.63     3.81   3.60   3.51 yield   2,110    3,080  6,080  5,760 2       2.5     20,400   44,000 225,600 249,600 5       13,400   27,600 136,800 150,400 10      10,200   18,900 86,800 10,800 20      7,850    13,800 56,600 71,200 R       2.60     3.19   3.99   3.51 yield   350      820    4,440  4,960 3       2.5     22,800   40,000 313,600 304,000 5       19,000   32,200 217,600 202,400 10      16,300   26,100 110,400 137,600 20      14,700   22,950 81,400 102,800 R       1.55     1.83   3.85   2.96 yield   190      490    4,800  5,080 ______________________________________ Spindle #6 for Initial and 1 day; Spindle #7 for all other samples.

Panel and topcoat testing revealed that good panel adhesion still was present but that the wet-on-dry topcoats (121.degree. C. for 30 minutes) were slightly tacky. The reason for the dimunition in performance of this butyl ether solvent compared to the ethyl ether version is not understood presently. Formulation No. 204 (wt.-parts) Ingredient*    103-1  103-2  105-1 105-2 138-1 138-2 ______________________________________ Occidental 6482 60     60     60   60   60   60 Borden VC265   40     40     40   40   40   40 CaCO.sub.3     100    100    100  100  200  200 Talc           20     20     20   20   --   -- Silica         1      1      1    1    --   -- DIDP           30     20     50   30   90   80 DHP            30     20     25   30   --   -- Monoisopropyl biphenyl 20     30     --   --   --   -- Propylene glycol diben- 20     30     --   --   --   -- zoate Ethyle toluene sulfon amide --     --     25   40   --   -- (ortho and para isomer mixture) Ethoxylated nonyl phenol --     --     --   --   10   20 ______________________________________ *Euretek 580 promoter added at 1% by weight in all formulations. Ethoxylated nonyl phenolIgepal CO630 nonylphenoxy poly(ethyleneoxy) ethanol, GAF Corporation.

While the aromatic ester, the sulfonamide, and the nonyl phenol solvents all solvated the adhesion promoter, wet-on-dry paintability was lacking. Ester solvents appear not to be beneficial due to postulated undesirable interaction with other ingredients. The sulfonamide solvent adds more amine value to the plastisol which is not desirable for achieving cure of the acid catalyzed topcoat. The ethoxylated nonyl phenol solvent should have functioned properly according to current understanding of the invention. Perhaps different levels or degrees of ethoxylation will enable this solvent to function is plastisol.

## Claims

1. In a plastisol composition comprising finely-divided vinyl chloride polymer, filler, a primary plasticizer, and a polyaminoamide-polyimidazoline adhesion promoter, the improvement for overcoating said plastisol with an acid catalyzed topcoat which comprises: adhesion promoter, and an effective amount of a secondary plasticizer nonionic solvent effective for solvating said adhesion promoter in said plasticizer/promoter phase, said plasticizer/promoter phase being preformed for addition with the remaining ingredients of the plastisol composition.

2. The plastisol composition of claim 1 wherein said secondary plasticizer nonionic solvent ranges from between about 10 to about 70 weight parts per 100 weight parts of said vinyl chloride polymer.

3. The plastisol composition of claim 1 wherein said primary plasticizer ranges from between about 20 and 200 weight parts per 100 weight parts of said vinyl chloride polymer.

4. The plastisol composition of claim 1 wherein said adhesion promoter ranges from between about 1 and 10 weight parts per 100 weight parts of said vinyl chloride polymer.

5. The plastisol composition of claim 1 wherein said secondary plasticizer nonionic solvent is selected from the group consisting of monoisopropyl biphenyl, diethylene glycol monoethyl ether, diisopropyl biphenyl, phenylxyleyl ethane, butylated biphenyl, and mixtures thereof.

6. The plastisol composition of claim 1 which contains more than one of said vinyl chloride polymer.

7. The plastisol composition of claim 1 which additionally comprises a thixotropic agent ranging from between about 1 and 5 weight parts per 100 weight parts of said vinyl chloride polymer.

8. A method for making a plastisol composition which comprises: a polyaminoamide-polyimidazoline adhesion promoter, and an effective amount of a secondary plasticizer nonionic solvent effective in solvating said adhesion promoter in said plasticizer/promoter phase; chloride polymer and a filler to make said plastisol composition.

9. The method of claim 8 wherein said secondary plasticizer nonionic solvent ranges from between about 10 to about 70 weight parts per 100 weight parts of said vinyl chloride polymer.

10. The method of claim 8 wherein said primary plasticizer ranges from between about 20 and 200 weight parts per 100 weight parts of said vinyl chloride polymer.

11. The method of claim 8 wherein said adhesion promoter ranges from between about 1 and 10 weight parts per 100 weight parts of said vinyl chloride polymer.

12. The method of claim 8 wherein said secondary plasticizer nonionic solvent is selected from the group consisting of monoisopropyl biphenyl, diethylene glycol monoethyl ether, diisopropyl biphenyl, phenylxyleyl ethane, butylated biphenyl, and mixtures thereof.

13. The method of claim 8 which contains more than one of said vinyl chloride polymer.

14. The method of claim 8 which additionally comprises a thixotropic agent ranging from between about 1 and 5 weight parts per 100 weight parts of said vinyl chloride polymer.