On the road to improved scratch resistance

Desmodur

Desmophen

On the road to improved scratch resistance

Dr. U. Meier-Westhues, Dr. Markus Mechtel, Thomas Klimmasch, Dr. Jrg Tillack

PUR clearcoats excel by their high resistance against acid rain (etching) and other chemicals. The appropriate selection of polyol and polyisocyanate allows deliberate control of hardness, glass transition temperature and resistance features. With increasing hardness e.g. the etch resistance rises and the scratch resistance reduces. Overcoming this difficulty of diverging scratch resistance and etch resistance will only be possible through increasing the cross-linking density while at the same time keeping a low Tg. The use of tailor-made polyols could lead to car clear coatings with increased scratch resistance in a relatively short time. Polyurethane clearcoats were used for the first time in automotive OEM (Original Equipment Manufacturing) around the mid nineteen eighties. Due to their extraordinarily high quality level they quickly spread and today, around 20% of all vehicles produced world-wide are coated with 1Component- and 2Component-PUR clearcoats. Today, 2C-PUR clearcoats lead to the highest quality levels, 1C-PUR systems on the basis of blocked polyisocyanates do not quite reach this level, however, they are often a good compromise between relatively easy processability and quality demands.

Desmodur
2C-PUR Polymer 1C-PUR 130 150 C HBL 80 140 C

Desmophen

Polymer

Polymer

Polymer

Figure 1: Reaction mechanisms of 2C-PUR and 1C-PUR systems

Figure 2: Amtec Kistler laboratory car wash

With increasing hardness the etch resistance rises and the scratch resistance by contrast falls
PUR clearcoats excel by their high resistance against acid rain (etching) and other chemicals. Here, they are clearly better than customary polyacrylate/melamineformaldehyde resin systems (Thermo Setting Acrylics = TSA). This is attributable to the urethane bonding which is extremely stable towards acids. The careful selection of polyol and polyisocyanate in 2C-PUR formulations allows deliberate control of the hardness, the glass transition temperature and the resistance characteristics. Test results have shown that with increasing hardness the etch resistance rises (not due to chemical changes but rather as a consequence of decreasing soakability) however, the scratch resistance by contrast falls. When improving the scratch resistance we must overcome this reversal effect without negative influence on the etch resistance. The etch resistance is tested by laying out coated panels in Jacksonville, Florida, for 14 weeks. The extent of etching spots is visually evaluated. The following scratch resistance results (Table 1 and Table 2 next sides) originate from practical data from a car wash test series after brush cleaning. The practical behavior of the clearcoats can be simulated by certain laboratory test methods. The gradient oven method to define the etch resistance as well as the Amtec Kistler laboratory car wash have become established mainly in Europe. The gradient oven method determines the minimum temperature necessary for the acid to cause coating damage after a defined exposure time. Depending on the specification, sulfuric acid or special acid mixtures are used. The Amtec Kistler laboratory car wash (Figure 2) works like a real car wash with polyethylene brushes that rotate over the test panels. Quartz is normally used as scratching medium today. The method is described in the DIN standard 55668. The correlation between car wash and Amtec Kistler is understandable, yet in both cases relatively hard parts such as sand or quartz affect the coating. In America the Crockmeter method has become standard to determine the scratch resistance. In this method the test panel is scratched with woolfelt following the ASTM D 6279-98. And non-silicate materials such as feldspar or calcite are used as abrasive media. The results of the Crockmeter method make obvious that this method doesnt correlate with the practical results from the car wash and consequently even not with the Amtec Kistler method. In contrast to the practical test where the TSA clearcoat is scratched most heavily, this clearcoat shows the best results in the Crockmeter method.

Table 1: Characterization of the clearcoat systems System [1] 2C-PUR flexible Desmophen A 870 Desmophen VP LS 2971 Desmodur N 3390 Pendulum hardness (Knig) [s] Glass transition temperature Tg max E1(DMA) [ C] Etching test Jacksonville/FL (14 weeks summer) Car Wash (10 cycles) Gloss retention [%] [2] 2C-PUR semi hard Desmophen A 870 Desmodur N 3390 [3] 2C-PUR hard Desmophen A 870 Desmodur N 3390 Desmodur Z 4470 [4] TSA Polyacrylate/ Melamine resin

87

130

170

160

30

55

80

30 70

4
0 = very good/10 = bad

10

89

87

84

85

Figure 3: Plastic deformation and fracture

Maximum reflow

Plastic deformation T > Tg

Minimum reflow

Fracture T > Tg 4

Desmodur
Table 2: Etch and scratch resistance System [1] 2C-PUR flexible Desmophen A 870 Desmophen VP LS 2971 Desmodur N 3390 Etching test Jacksonville/FL (14 weeks summer) Gradient oven test 30 min, 1 % H2SO4 [C] Car Wash (10 cycles) Gloss retention [%] Amtec Kistler 10 cycles Gloss retention [%] Crock meter Gloss retention [%] [2] 2C-PUR semi hard Desmophen A 870 Desmodur N 3390

Desmophen

[3] 2C-PUR hard Desmophen A 870 Desmodur N 3390 Desmodur Z 4470

[4] TSA Polyacrylate/ Melamine resin

4
0 = very good/10 = bad

10

41

45

49

36

89

87

84

85

71

68

60

51

90

83

77

95

Nano scratch method allows differentiation between plastic deformation and fracture
To clarify the apparently contradictory results the nano scratch method is used. This method allows the differentiation between plastic deformation and irreversible fracture as possible scratching causes (Figure 3). Scratches caused by plastic deformation are produced by relatively low loads. The coating deforms only plastically under the effect of the scratching medium. When heating above glass temperature the plastic deformation largely recovers due to its viscoelasticity. This phenomenon of self-healing or recovering is well known and is especially observed with coatings on PUR basis in the field. Stronger forces eventually lead even to an irreversible damage of the coating, the so called fracture. A self-healing or recovering of this scratch type is possible to a very minimal extent only.

Figure 4: CSEM Nano scratch tester (measuring principle/evaluation criteria)

Cantilever tip (indentor) Z progressive load

Coating

Substrate (panel)

Normal force [mN]

cracks

5 mN

Scratch length [mm] X Flat sample recipient (stage) movable in x/y direction

The nano scratch method (Figure 4) produces a single scratch in the coating using an indentor with increasing normal load. The method is accompanied by atomic force microscopy. The critical load is ascertained at which a fracture occurs in the film for the first time. Additionally the residual depth, so the plastic deformation, is measured under a load which is clearly below the critical load (here 5 mN). All of the PUR systems 1 to 3 show a higher plastic deformation (residual depth) than the TSA system 4 (Table 3).

This has an effect under Crockmeter scratching, which due to its working method using a relatively low normal load and relatively soft abrasion medium essentially causes plastic deformation. The recovery behavior of the coating after 1h 70C treatments can be used as proof for this. The selfhealing behavior of the PUR systems is so strongly developed that all the films recover almost to the initial value. A scratching is visually no longer detectable. In contrast the TSA system 4 was partly irreversibly scratched already under relatively careful conditions of the Crockmeter method, the systems recovers only slightly.

Desmodur

Desmophen

Topography at 5 mN Progressive load

Point of fracture

Here, it becomes obvious that systems which recover well from Crockmeter scratching must show a low plastic deformability. However, with these test parameters the Crockmeter method is not suitable to simulate the relatively hard conditions of the car wash. The critical load values from the nano scratch method imply for the PUR systems 1 and 2 a clearly less inclination to fractures of these systems compared with the hard PUR system 3 and the TSA system 4. Both the practical test and the Amtec Kistler method proved the result from the nano scratch examinations. The PUR systems 1 and 2 are clearly superior to the hard PUR system 3 and the TSA system 4.

Concept: To increase the cross-linking density in the film and to keep the Tg largely constant
It appears that cross-linking density and glass transition temperature [Tg] oppose each other in influence on scratch resistance. High cross-linking density leads to higher scratch resistance, whereas a high Tg has the opposite effect. The approach to further increase the scratch resistance of PUR clearcoats starts from the idea to increase the crosslinking density in the film and, however, to keep the Tg largely constant (Table 4).

Table 3: Comparison of scratching methods System [1] 2C-PUR flexible Desmophen A 870 Desmophen VP LS 2971 Desmodur N 3390 Nano scratch tester Critical load [mN] Residual depth at 5 mN [m] Crockmeter Direct Gloss retention [%] 1 h 70 C Gloss retention [%] Amtec Kistler Direct Gloss retention [%] 1 h 70 C Gloss retention [%] Car wash 10 cycles Gloss retention [%] 17 cycles Gloss retention [%] [2] 2C-PUR semi hard Desmophen A 870 Desmodur N 3390 [3] 2C-PUR hard Desmophen A 870 Desmodur N 3390 Desmodur Z 4470 [4] TSA Polyacrylate/ Melamine resin

28.7 0.59

19.4 0.64

15.0 0.54

11.9 0.38

90 100

83 99

77 97

95 97

71 76

68 72

60 61

51 52

89 96

87 93

84 90

85 89

Similar to system 2, the system 5 formulation is based on the combination of Desmodur N 3390 und polyacrylate, however, due to increased concentrations of urethane bondings it shows a higher cross-linking density. Through targeted setting of the polyacrylate combination, the Tg of the coating could be increased only from 55C to 65C. However the crosslinking density could be increased from 900 g/mol to 680 g/mol.

In comparison to system 2 system 5 shows a reduced residual depth. After Crockmeter scratching the system is clearly less scratched than system 2. After recovery the system recovered nearly completely. Obviously, the Crockmeter method works so carefully that it doesnt simulate the realistic scratching conditions e.g. in a car wash. Conspicuous is the significantly increased value of the critical load. So, the highly cross-linked system 5 is irreversibly scratched at relatively high loads only. This becomes clear in the examinations following Amtec Kistler. This system behaves clearly more favorably than system 2 with a conventional cross-linking density. Etch resistance, however, remains on the same high level.

Desmodur
Table 4: Influence of the cross-linking density on the technological characteristics System [2] 2C-PUR semi hard standard cross-linking density Tg [ C] Nano scratch tester Critical load [mN] Residual depth at 5 mN [m] Crockmeter Direct Gloss retention [%] 1 h 70 C Gloss retention [%] Amtec Kistler Direct Gloss retention [%] 1 h 70 C Gloss retention [%] Car wash 10 cycles Gloss retention [%] 17 cycles Gloss retention [%] Gradient oven test 30 min, 1 % H2SO4 [C] [5] 2C-PUR semi hard

Desmophen

[6] 2C-PUR waterborne

increased cross-linking density

55 19.4 0.64

65 28.7 0.55

57 27.0 0.047

83 99

90 99

89 94

68 72

81 85

76 78

89 93 45

93 96 44

91 94 45

The proof of quality improvement must eventually be provided in the field. Of all systems tested the coating on basis of the highly cross-linked 2C-PUR version (system 5) is the best. After 10 and 17 car wash cycles the relative gloss retention still is 93% and 96%, respectively. The principle of increasing the cross-linking density with only a modest increase in glass transition temperature Tg seems to prove successful to further increase the quality of PUR clearcoats. Also the water reducible 2C-PUR system 6 shows interesting characteristics. The basis is a polyacrylate/polyurethane dispersion which is crosslinked with the hydrophobic HDI-trimer Desmodur N 3600. The systems Tg is about 57 C at a crosslinking density of 800 g/mol.

Even in long-term developments to improve scratch resistance the principle of increasing the crosslinking density is used. Very promising are the so-called Dual Cure systems. They are 2C-PUR clearcoats which are partly UV-cross-linked as well as thermally hardened. In particular radiation hardening systems are known for their high cross-linking density. In clever combination with thermal hardening the correct balance regarding flexibility and hardness should be achieved. In addition the thermal hardening through polyol/polyisocyanate reaction which takes place at room temperature, provides a sufficient quality even in the shadow areas of the coating.

Results at a glance
Around 20% of all vehicles produced worldwide are coated with 1C and 2C polyurethane based coatings due to their extraordinarily high quality level. PUR clearcoats excel by their high resistance against acid rain (etching) and other chemicals and are clearly superior to the customary TSA clearcoats, here. The appropriate selection of polyol and polyisocyanate allows deliberate control of hardness, glass transition temperature and resistance features. With increasing hardness e.g. the etch resistance rises and the scratch resistance reduces. Overcoming this difficulty of diverging scratch resistance and etch resistance will only be possible through increasing the cross-linking density while at the same time keeping a low Tg. The use of tailor-made polyols could lead to car clear coatings with increased scratch resistance in a relatively short time. The water reducible 2C-PUR clearcoat is an alternative of equal quality and less VOC to the high solid 2C-PUR clearcoats.

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Desmodur

Desmophen

Another approach to improve the scratch resistance while keeping the etch resistance is the use of UV technology. Mainly Dual Cure systems combine the advantage of high cross-linking density from the UV technology with the flexibility and shadow hardening of the 2C-PUR technology.

A comparison of the different scratching methods shows that the nano scratch method is the scientifically most substantial one. When producing single scratches the parameters such as residual depth and critical load are ascertained that characterize the physical behavior of a coating. The Crockmeter test is a very careful scratching method which mainly leads to plastic deformations. Hard scratching conditions such as in a car wash are not simulated with this method. Field tests and Amtec Kistler laboratory car wash results correlate well. In both cases there are hard scratching conditions which lead both to plastic deformation and fracture to an essential portion.

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