RADIATION CURABLE COMPOSITION

Abstract

The present invention provides a radiation curable composition comprising a hydroxyl functional urethane (meth)acrylate compound (A) having an hydroxyl value between 10 and 80 mg KOH/g and which is the reaction product of a hydroxyl functional (meth)acrylate compound (A1) obtained from the reaction a or b: a. at least one diepoxy functional compound (A11a) with a (meth)acrylate compound (A11b) comprising at least one (meth)acrylate group and one carboxylic acid functional group or b. a carboxylic acid functional compound (A12a) comprising two carboxylic acid groups with an epoxy (meth)acrylate compound (A12b) comprising one glycidyl group and at least one (meth)acrylate group, with a diisocyanate functional compound (A3), and optionally a compound (A2) different of compound (A1) comprising two hydroxyl groups. Such composition is useful for example for dual curable compositions or for thick pigmented systems.

Claims

1. A radiation curable composition comprising a hydroxyl functional urethane (meth)acrylate compound (A) having an hydroxyl value between 10 and 80 mg KOH/g and which is the reaction product of a hydroxyl functional (meth)acrylate compound (A1) obtained from the reaction a orb: at least one diepoxy functional compound (A11a) with a (meth)acrylate compound (A11b) comprising at least one (meth)acrylate group and one carboxylic acid functional group or a carboxylic acid functional compound (A12a) comprising two carboxylic acid groups with an epoxy (meth)acrylate compound (A12b) comprising one glycidyl group and at least one (meth)acrylate group, with a diisocyanate functional compound (A3), and optionally a compound (A2) different of compound (A1) comprising two hydroxyl groups.

2. A radiation and thermally curable composition comprising: at least one hydroxyl functional urethane (meth)acrylate compound (A) as defined in claim 1, at least one isocyanate functional compound (B) comprising at least one isocyanate group and optionally at least one (meth)acrylate group, optionally at least one compound (C) different from compound (A) which compound (C) comprises at least two hydroxyl groups suitable for polyaddition with compound (B) and optionally comprises at least one (meth)acrylate group, optionally at least one (meth)acrylate compound (D) which is substantially free of any chemical group reactive to hydroxyl groups of compounds (A) and (C) and to isocyanate group of compound (B).

3. The curable composition according to claim 1, wherein compound (A) has a number average molecular weight of 1500 to 20 000 g/mol, preferably 2000 to 20 000 g/mol, and an amount of ethylenically unsaturated groups comprised between 0.5 and 3.5 milli-equivalent per gram of solid material.

4. The curable composition according to claim 1, wherein compound (A1) comprises at least one aliphatic or aromatic cycle.

5. The curable composition according to claim 1, wherein compound (A1) is a reaction product of a diepoxy compound (A11a) with compound (A11b).

6. The curable composition according to claim 5, wherein compound (A11a) is a cycloaliphatic epoxy compound.

7. The curable composition according to claim 6, wherein compound (A11a) is hydrogenated bisphenol A diglycidyl ether (HBADGE).

8. The curable composition according to claim 5, wherein compound (A11b) is (meth)acrylic acid.

9. The curable composition according to claim 1, wherein compound (A1) is present in at least 50 w % relative to the total amount of compounds (A1) and (A2).

10. The curable composition according to claim 1, wherein the number average molecular weight of compound (A) is at least 1500 g/mol, preferably at least 2000 g/mol, more preferably at least 2500 g/mol.

11. The curable composition according to claim 1, wherein the hydroxyl value of compound (A) is comprised between 10-80 mg KOH/g, preferably between 15-80 mg KOH/g, more preferably between 20-70 mg KOH/g of solid material.

12. Use of a curable composition according to claim 1 for dual cure application, for conformal coating, for composites, for three dimensional (3D) applications, for thick pigmented systems, for thermoforming, for thermoformable inks or for molding applications.

13. Use of a radiation curable composition according to claim 1 in a thermoforming or molding process for producing a shaped article by molding or thermoforming a substrate, film or foil.

14. Use of a radiation curable composition according to claim 1 in a thermoforming or molding process for producing a shaped article by molding or thermoforming a substrate, film or foil, wherein the substrate, film or foil is coated with the curable composition according to claim 1, thermoformed and the thermoformed article is subsequently exposed to actinic radiation.

15. Substrate, film or foil printed or coated with a curable composition according to claim 1.

Description

EXAMPLES

Experimental Data

[0117] List of materials: [0118] ABS: Acrylonitrile butadiene styrene, Magnum 3616, Dow [0119] PC: Polycarbonate, Lexan 9030, Sabic. [0120] ABS/PC: Bayblend T85, Bayer [0121] AA: acrylic acid, monomer, BASF [0122] Veralite® 200: thermoformable plastic sheet based upon PETG (Glycol modified Polyethylene Terephthalate), IPB [0123] Eponex® 1510, hydrogenated bisphenol A diglycidyl ether, Hexion [0124] BAC: butyl acetate, solvent, Celanese. [0125] IPDI: isophorone diisocyanate, Evonik [0126] HDI: hexamethylene diisocyanate, Covestro [0127] Desmodur® N 3300: Aliphatic polyisocyanate (HDI trimer), Covestro. [0128] PETIA: pentaerythritol triacrylate, allnex. [0129] Eternacoll® PH100: copolycarbonate diol, UBE [0130] Eternacoll® PH200D: copolycarbonate diol, UBE [0131] Eternacoll® PH300D: copolycarbonate diol, UBE [0132] EBECRYL® 1200: acrylate functional acrylic resin, allnex [0133] EBECRYL® 4510: isocyanate functional urethane acrylate, allnex [0134] BHT: butylated hydroxytoluene, stabilizer, Innochem. [0135] MeHQ: Hydroquinone Monomethyl Ether, stabilizer, Innochem [0136] Hycat OA: catalyst, Dimension Technology Chemical Systems, Inc. [0137] PTZ: phenothiazine, Allessa [0138] Valikat ZB8: PU catalyst, Umicore. [0139] Additol® CPK: 1-hydroxy-cyclohexylphenyl-ketone, photoinitiator, Allnex. [0140] DBTL: dibutyl tin dilaurate, catalyst, Vesta Intracon. [0141] Modaflow® 9200: Acrylic flow modifier, without silicone addition, Allnex. [0142] Tegowet® 270, polyether siloxane copolymer, Evonik [0143] Syloid MX 309: silica matting agent, Grace [0144] Acematt OK 520: wax treated silica matting agent, Evonik [0145] Lanco™ PP 1362 D: Modified Polypropylene Wax, Lubrizol

[0146] The Measurements were Done According to Following Standards:

[0147] Hydroxyl values (10H in mg KOH/g) were measured using the following method. This “OH Number” method covers the automated quantification procedure for hydroxyl groups by means of potentiometric titration. The hydroxyl number is defined as the number of milligrams of potassium hydroxide required to neutralize the hydrolysis product of the fully acetylated derivative prepared out of one gram of -resin. Step 1-Acetylation step: All hydroxyl functions are acetylated at 75° C. by acetic chloride. Step 2-Hydrolysis step: The excess of acetic chloride is hydrolyzed by a solution of N-methyl-2-pyrrolidone (NMP) in water. Step 3-Titration step: The formed acid functions are titrated with KOH 0.5 N solution.

[0148] The viscosity of the resin is measured at a fixed shear rate with a cone and plate type rheometer MCR100 (Paar-Physica) according to DIN EN ISO 3219, 25 1/s; 23° C.

[0149] The number-average molecular weight (Mn) was determined by conventional gel permeation chromatography (GPC) with Polystyrene standards EasyCal from Polymer Laboratories (Molecular Weight range: 200-400.000 g/mol). The sample was dissolved (1.0% wt./wt.) in tetrahydrofuran (THF) containing 0.5% toluene as Flow rate marker. Analysis were performed by liquid chromatography (Merck-Hitachi L7100) equipped with 3 PLGel Mixed-D LS polystyrene divinylbenzene GPC columns (300×7.5 mm×5 μm). The components of the sample were separated by the GPC columns based on their molecular size in solution and detected by a Refractive Index detector. Data were gathered and processed by Polymer Laboratories Cirrus GPC software.

[0150] Preparation of Urethane Acrylate (A) According to the Present Invention

[0151] Step 1: Preparation of epoxy acrylate (A1): 363.5 g of Eponex® 1510, 0.48 g BHT and 0.36 g Hycat OA were charged into a reaction flask equipped with an agitator, liquid addition funnel and thermometer. This mixture was heated at 95° C. An addition funnel is filled with a mixture of 120.4 g AA, 0.48 g MeHQ and 0.36 g Hycat OA which was added dropwise to the reaction flask over a period of 2 hours so that the temperature in the reaction flask does not exceed 105° C. After all AA was added, the reaction mixture was further stirred at 110° C. until the acid value was lower than 1 mg KOH/g and the epoxy value was lower than 0.27%.

[0152] Step 2—Preparation of urethane acrylate (A): Epoxy acrylate (A1) prepared in step 1 was cooled down to 60° C. and 396 g BAC, 0.2 g Valikat ZB8 and 0.15 g of PTZ was added and stirred for 15 minutes. After this 107.5 g HDI was added in 3 different portions and the reaction mixture was subsequently further reacted until a specific isocyanate content of not more than <0.1% was reached. The product had a hydroxyl value of 50 mg KOH/g on solids, a viscosity of 1450 mPa.Math.s measured at 25° C. and a number average molecular weight of 2940 g/mol.

[0153] Example 2: similar as example 1 but with IPDI instead of HDI.

[0154] Example 3-5, similar as example 1 but with different ratio's between HDI and the epoxy acrylate (A1) resulting in urethane acrylates with a different number average molecular weight.

[0155] Examples 6 and 7 are similar as example 1 but respectively 20 and 50 w % of polycarbonate diol (Eternacoll PH100) was used together with respectively 80 w % and 50 w % of the epoxy acrylate.

[0156] The types and amounts of reagents used to prepare synthesis examples 1-7 are summarized in Table 1

TABLE-US-00001 TABLE 1 Ex 1 Ex 2 Ex 3 Ex 4 Ex 5 Ex 6 Ex 7 Step 1 Epoxy acrylate (A1) 486.3 486.3 486.3 486.3 486.3 486.3 486.3 Step 2 BAC 396.0 418.6 400.8 404.0 388.1 486.6 758.1 Valikat ZB8 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Eternacoll PH 100 121.6 486.3 HDI 107.5 114.7 119.5 95.6 121.7 164.3 IPDI 141.4 Hydroxy value 50 48 43 37 68 47 45 (mg KOH/g on solid material) Viscosity mPa, s 1450 1820 2350 3100 850 1400 1550 at 25° C. Number average 2940 2935 3510 3940 2420 3445 3845 molecular weight (g/mol) Double bond 2.82 2.67 2.79 2.76 2.88 2.29 1.47 content (meq/g on solid material) Physical drying yes yes yes yes no no no

[0157] In comparative examples 1 and 2 the urethane (meth)acrylate according to present invention was exchanged with a polycarbonate diol compound respectively Eternacoll PH200D and Eternacoll PH300D. Eternacoll PH200D and Eternacoll PH300D do not contain an acrylate functionality and have a number average molecular weight of respectively 2000 and 3000 g/mol and a hydroxy value of respectively 58 and 39 mg KOH/g.

[0158] Comparative example 3 was EBECRYL® 1200 which is an acrylate functional acrylic resin supplied in 45% by weight of BAC with a number average molecular weight of 6420 g/mol and a hydroxy value on solid material of 200 mg KOH/g. EBECRYL® 1200 is physical drying.

[0159] Comparative example 4 was epoxy acrylate (A1) from step 1 diluted with BAC with no further reaction with a diisocyanate and number average molecular weight of 815 g/mol.

[0160] In comparative example 5 the epoxy acrylate (A1) was reacted with HDI and had a number average molecular weight of 1815 g/mol.

[0161] The types and amounts of reagents used to prepare synthesis comparative examples 4-5 are summarized in Table 2.

TABLE-US-00002 TABLE 2 Comp Comp Ex 4 Ex 5 Step 1 Epoxy acrylate (A1) 486.3 486.3 Step 2 Butylacetate 324.4 372.1 Valikat ZB8 0.2 0.2 hexamethylene diisocyanate — 71.7 Hydroxy value 186 98 (mg KOH/g on solid material) Viscosity mPa,s at 25° C. 300 88 Number average Mw (g/mol) 815 1815 Double bond content 3.44 3 (meq/g on solid material) Physical drying no no

[0162] Preparation of Isocyanate Functional Urethane Acrylate (B)

[0163] Synthetic example 8: 371 g of PETIA, 429 g Desmodur N3300, 200 g BAC together with 100 ppm of PTZ was charged in a reaction flask equipped with a mechanical stirrer, a condenser and gas in and outlet. The reactants were stirred in air atmosphere at room temperature and afterwards heated to 60° C. and held for 18 hours. The product had a viscosity of 1600 mPa.Math.s at 25° C. and an isocyanate content of 6.2%.

[0164] As a second isocyanate functional urethane acrylate EBECRYL® 4510 is taken. EBECRYL® 4510 had a viscosity of 20000 mPa.Math.s at 23° C. and an isocyanate content of 7%.

[0165] Resin Evaluation

[0166] Preparation of the Radiation Curable Composition—2K Composition

[0167] Radiation curable compositions F1 to F10 according to the invention and comparative radiation curable composition Comp F1 to F6 were prepared by using the amounts and the type of compounds as summarized in table 3, 4 and 5.

TABLE-US-00003 TABLE 3 formulation examples F1-F6 Amounts in grams Ex F1 Ex F2 Ex F3 Ex F4 Ex F5 Ex F6 Component I Synth Ex 1 76.9 Synth Ex 2 78.2 Synth Ex 3 80.8 82.4 Synth Ex 4 83.5 Synth Ex 5 70.8 BAC 5 5 5 5 5 5 DBTL 0.02 0.02 0.02 0.02 0.02 0.02 Modaflow ®9200 0.5 0.5 0.5 0.5 0.5 0.5 Tegowet ® 270 0.8 0.8 0.8 0.8 0.8 0.8 Additol ® CPK 3 3 3 3 3 3 Component II Synt Ex 8 23.1 21.8 19.2 16.5 29.2 EBECRYL 17.6 4510 BAC 5

TABLE-US-00004 TABLE 4 formulation examples F7-F10 Amounts in grams Ex F7 Ex F8 Ex F9 Ex F10 Component I Synth Ex 3 62.6 37.4 Synth Ex 6 78.2 Synth Ex 7 80.8 Eternacoll 15.7 37.4 PH200D/BAC (60/40) BAC 5 5 5 5 DBTL 0.02 0.02 0.02 0.02 Modaflow ® 09200 0.5 0.5 0.5 0.5 Tegowet ® 270 0.8 0.8 0.8 0.8 Additol ® CPK 3 3 3 3 Component II Synt Ex 8 21.8 19.2 21.7 25.2 In formulation ex 9 and 10 an extra polyol compound C was added being a difuntional polycarbonate diol (Eternacoll PH200D).

TABLE-US-00005 TABLE 5 comparative formulation examples F1-F6 Amounts in grams Comp F1 Comp F2 Comp F3 Comp F4 Comp F5 Comp F6 Component I Eternacoll 69.7 PH200D/BAC (60/40) Eternacol 63.6 PH300D/BAC (60/40) EBECRYL 1200 42.1 80 Comp Ex 4 61.4 Comp Ex 5 33.6 BAC 5 5 5 5 5 5 DBTL 0.02 0.02 0.02 0.02 0.02 0.02 Modaflow ®9200 0.5 0.5 0.5 0.5 0.5 0.5 Tegowet ® 270 0.8 0.8 0.8 0.8 0.8 0.8 Additol ® CPK 3 3 3 3 3 3 Comp. II Synth Ex 8 30.3 36.4 57.9 20 38.6 66.4

[0168] Assessment of the Properties of the Radiation Curable Compositions

[0169] Films were prepared with the radiation curable compositions. The coating layers were applied on substrates using a bar coater. Solvent flash off and thermal treatment was done in a ventilated oven at 80° C. for 30 min. The target coating thickness after solvent flash is 15 μm. Directly after the thermal treatment step the coatings were evaluated on being touch dry and blocking resistance.

[0170] Thermoforming was assessed on Veralite 200 substrate after storage of one week at room temperature.

[0171] Other properties (Film appearance, adhesion, abrasion resistance, scratch resistance, hydrolysis resistance, hand crème and sun tan lotion resistance) were tested on substrates that were thermally treated in ventilated oven at 80° C. and subsequently cured under UV lights at a cure speed of 2×5 m/min using a 120 Watt/cm.sup.2 Hg lamps. Prior to the testing the substrates were stored for 1 week at room temperature. Substrates used are PC, ABS, ABS/PC. All the films obtained show nice, clear aspect without defects, before and after the oven and after UV curing.

[0172] The properties of the radiation curable compositions were assessed according to the following methods:

[0173] Tackiness and film sticking after solvent evaporation and before curing: a film with a dry coating thickness of 15 μm is applied on a PC film and thermally treated for 30 minutes in oven at 80° C. Tackiness is evaluated by a finger pressing on top of the film surface. The results are recorded in a 1-5 scale: 0=wet/1=very tacky/2=tacky/3=slightly tacky/4=dust free-finger print/5=tack free. A 5 score corresponds to a tack free film, when no visible marks appear on the surface. In addition film stickiness is evaluated after two films are put on contact and separate from each other. The results are recorded in a 0-3 scale: 0=very strong stickiness/1=strong stickiness/2=slightly stickiness/3=no stickiness.

[0174] Blocking resistance: a film with a dry coating thickness of 15 μm is applied on a PC film and thermally treated for 30 minutes in an oven at 80° C. After cooling down and storage of the cured sample, surfaces are put face to face on their coated sides for 2 hours in an oven at 45° C. with pressure of 1 kg on a surface of 6 cm diameter. Rating for the blocking resistance is recorded in a 0-5 scale: 5=no blocking, no defect/4=little bit of blocking but no defect/3=minor defect/2=major defect/1=cannot be separated.

[0175] Thermoformability: a film with a dry coating thickness of 15 μm is applied on Veralite 200 substrate and thermally treated for 30 minutes in an oven at 80° C. After cooling down and storage of the substrate at room temperature the substrate is tested on its thermoformability using a mold (massive cylinder with diameter of 4.5 cm and a height of respectively 3.5 and 8 cm corresponding to approximately a maximum elongation of respectively 150%, 250% and 300%) in a thermoforming plant (vacuum former 725 FLB). After the film being thermoformed the coating is evaluated on its aspect and rated from 1 to 5: 5—no defects, 4—few small cracks, 3—lot of small cracks, 2—large cracks and coating delamination at zone with largest elongation, 1—large cracks and delamination over the full moulded area.

[0176] Film appearance (transparency): the transparency of the coating is assessed on the difference aspect. The results are rated visually and recorded in a 1-5 scale: 5=fully transparent; 4=very slightly hazy; 3=slightly hazy; 2=hazy; 1=opaque. A high value (5) is expected to provide the best appearance and functionality of the coated object.

[0177] Adhesion (cross hatch tape): The adhesion on ABS, PC and ABS/PC is assessed using the cross-cut test according to ISO 2409. 5 cuts of −1 cm long and spaced by −1 mm are made in the coating using a knife, followed by 5 similar cuts in the transversal direction. The adhesion was measured using an adhesive tape (Scotch®) firmly pressed on the cross-cut coating and removed rapidly; the damage to the cross-cut surface area of the coating due to adhesion loss is expressed in a 0-5 scale, 5=best. A high adhesion is necessary to ensure a strong permanent bond between the coating and the substrate.

[0178] Hand cream and suntan lotion resistance: coating's resistance and cream and sun lotion is evaluated according to VW PV 3964. Sun cream and hand lotion are applied on a bandage and laid on the coating. Sample is placed in a ventilated oven for 24 hours at 80° C., the bandage is removed and the remnant of cream/lotion is wiped off with a tissue. The sample is left at least 4 hours at room temperature before evaluation. Coating is evaluated on visual damage and cross hatch adhesion after test. Test is passed when coating is not damaged and when same level of adhesion is achieved before and after the test.

[0179] Hydrolysis resistance: coating's resistance to hydrolysis is evaluated according to VW TL 226. The coating applied on a plastic substrate is place into a humidity chamber for 72 h, at 90° C., 95% relative humidity. Coating is evaluated on visual damage and cross hatch adhesion after humidity test. Test is passed when coating is not damaged and when same level of adhesion is achieved before and after the test.

[0180] Stain resistance: A product (Z) is put on the coating for a certain period of time (Y) and covered with a glass capping to prevent air drying. After time (Y) the product (Z) will be removed with a tissue drenched in solvent (S) or a water/soap solution. A scale from 1 to 5 is then used as following to determine and score the stain resistance (5: No visual stain, 4: very light stain, 3 moderate stain, 2: strong stain, 1: very strong stain. The following products (also called household stain marking substances) were tested

TABLE-US-00006 TABLE 6 Z Y S black marker (Artline 70 N) 5 minutes IPA eosine 16 hours H.sub.2O/detergent Iso-betadine 16 hours H.sub.2O/detergent Ethanol/water (50/50) 24 hours Dry wipe Red Wine 24 hours H.sub.2O/detergent Coffee 24 hours H.sub.2O/detergent NH3 (10%) 24 hours H.sub.2O Mustard 24 hours H.sub.2O/detergent

[0181] Abrasion (taber Haze): coating's resistance to abrasion is assessed with taber haze according to ASTM D1044. Initial coating haze on PC is measured. The test specimen is then placed on the abrasion tester. A 500 gram load is placed on top of abrader wheel CS-10F and allowed to spin for a specified number of revolutions. A final haze measurement is taken and is compared to initial value. Abrasive damage is visually judged and numerically quantified by the difference in haze percentage in accordance with Test Method D1003 between an abraded and unabraded specimen. The lower the percent haze difference, the more resistant the coating is to abrasive damage.

[0182] Scratch resistance (steel wool on PC): the test is performed by scratching the coating with the steel wool for 5 double rubs. The results are rated visually and recorded in a 1-5 scale: 5=no scratch; 4=very light scratch; 3=moderate scratch; 2=strong scratch; 1=very strong scratch. A high value (5) is expected to provide the best protection against any deterioration of the coated object.

[0183] Properties of the thermally cured coating are given in table 7 and 8.

TABLE-US-00007 TABLE 7 Compositions Ex F1 Ex F2 Ex F3 Ex F4 Ex F5 Ex F6 Ex F7 Ex F8 Ex F9 Ex F10 Tack free/ 5 5 5 5 5 5 5 5 5 3 fingerprint film sticking 3 3 3 3 3 3 3 3 3 1 Blocking resistance 45° C. 5 5 5 5 4 5 5 4 5 5 Thermoforming 8 cm (>300% 4 4 5 5 5 2 5 3 4 3 elongation) 5 cm (200% 5 5 5 5 5 3 5 4 5 4 elongation 3 cm (150% 5 5 5 5 5 5 5 5 5 5 elongation)

TABLE-US-00008 TABLE 8 Compositions Comp F1 Comp F2 Comp F3 Comp F4 Comp F5 Comp F6 Tack free/ 5 5 5 5 5 2 fingerprint film sticking 3 3 3 3 3 1 Blocking resistance 45° C. 5 4 5 5 5 2 Thermoforming 8 cm (>300% 2 5 1 1 1 1 elongation) 5 cm (200% 4 5 1 1 1 1 elongation 3 cm (150% 5 5 1 1 2 1 elongation)

[0184] We can conclude that coatings according to the present invention had good blocking resistance and good to excellent thermoformability. Comparative examples F3 and F4 based on EBECRYL 1200 having a high hydroxy value of 200 mg KOH/g (on solids) had very poor thermoformability. Comparative examples F5 and F6 had also bad thermoformability. These coatings were based on comparative synthesis examples 4 and 5 having also a high hydroxy value of respectively 186 and 98 mg KOH/g (on solids) and also a relatively low number average molecular weight respectively 815 g/mol and 1815 g/mol.

[0185] The properties of the UV cured coatings are given in tables 9 and 10:

TABLE-US-00009 TABLE 9 Compositions Ex F1 Ex F2 Ex F3 Ex F4 Ex F5 Ex F6 Ex F7 Ex F8 Ex F9 Ex F10 Adhesion — PC sheet Film appearance 5 5 5 5 5 5 5 4 4 2 Adhesion (cross hatch tape) 5 5 5 5 5 5 5 5 5 5 Black ABS/PC Film appearance 5 5 5 5 5 5 5 4 4 2 Adhesion (cross hatch tape) 5 5 5 5 5 5 5 5 5 5 Black ABS Film appearance 5 5 5 5 5 5 5 4 4 2 Adhesion (cross hatch tape) 5 5 5 5 5 5 5 5 5 5 Hand cream — resistance PC sheet Visual damage no no no no no no no no no yes Adhesion (cross hatch tape) 5 5 5 5 5 5 5 5 5 5 Black ABS Visual damage no no no no no no no no no yes Adhesion (cross hatch tape) 5 5 5 5 5 5 5 0 5 5 Suntan lotion — resistance PC sheet Visual damage no no no no no no no yes no yes Adhesion (cross hatch tape) 5 5 5 5 5 5 5 5 5 5 Black ABS Visual damage no no no no no no no yes no yes Adhesion (cross hatch tape) 5 5 5 5 5 5 5 5 5 5 Hydrolysis — resistance PC sheet Visual damage no no no no no no no no no no Adhesion (cross hatch tape) 5 5 5 5 5 5 5 5 5 5 Abrasion Scratch resistance (Steel 3 3 3 3 3 3 3 3 3 3 wool 5 double rubs) Abrasion 100 cycles   5.4 NA   6.5   6.2   7.2   6.1   6.3   5.3   7.5  10.3 (Taber Haze) 300 cycles   9.5 NA  11.8  10.9  11.5  10.4  12.0   9.9  12.5  14.4

TABLE-US-00010 TABLE 10 Compositions Comp F1 Comp F2 Comp F3 Comp F4 Comp F5 Comp F6 Adhesion — PC sheet Film appearance 5 5 5 5 5 5 Adhesion (cross hatch tape) 5 5 5 5 5 5 Black ABS/PC Film appearance 5 5 5 5 5 5 Adhesion (cross hatch tape) 5 5 5 0 5 5 Black ABS Film appearance 5 5 5 5 5 5 Adhesion (cross hatch tape) 5 5 5 5 5 5 Hand cream resistance — PC sheet Visual damage no no no no no no Adhesion (cross hatch tape) 5 5 5 5 5 5 Black ABS Visual damage yes no no no no no Adhesion (cross hatch tape) 4 5 5 5 5 5 Suntan lotion resistance — PC sheet Visual damage yes yes no no no no Adhesion (cross hatch tape) NA NA 5 5 5 5 Black ABS Visual damage yes yes no no no no Adhesion (cross hatch tape) NA NA 5 5 5 5 Hydrolysis resistance — PC sheet Visual damage no no no no no no Adhesion (cross hatch tape) 5 5 0 0 5 5 Abrasion Scratch resistance (Steel 3 3 4 3 3 3 wool 5 double rubs) Abrasion (Taber Haze) 100 cycles   5.6 NA   5.2 5   5.2   5.1 300 cycles  10.8 NA   8.7 9   9.3  10.1

[0186] Thus examples 1-10 according to present invention showed outstanding adhesion to the different plastic substrates, a moderate to good level of scratch and abrasion resistance and were passing all challenging chemical resistance tests typically used in automotive interior namely: the hydrolysis, hand cream and suntan lotion resistance. ExF9 and F10 show that thermoforming properties are maintained when component (C) is present in the composition, but some properties are decreased when using large amounts of (C) (ExF10).

[0187] Comparative formulation examples F1 and F2 based on polycarbonate diols Eternacoll PH200D and Eternacoll PH 300D failed in the suntan lotion resistance test. Comparative example F3 and F4 based on EBECRYL 1200 lost adhesion in the hydrolysis test.

[0188] Resistance to typical household stains was evaluated on both formulation example F3 which is cured thermally and with UV and F11, F12 which are only cured with UV.

[0189] A coating of 10p dry is applied by bar coater on a white Leneta paper. After solvent flash off for 5 min at 80° C. for F11 and F12 or solvent flash off and thermal treatment for 30 min at 80° C. for F3 in a ventilated oven, the coating was cured under UV lights at a cure speed of 2×5 m/min using a 120 Watt/cm.sup.2 Hg lamps. Prior to the testing the substrates were stored for 1 week at room temperature.

TABLE-US-00011 TABLE 11 Amounts in grams Ex F3 Ex F11 Ex F12 Component I Synth Ex 3 80.8 100 100 BAC 5 5 5 DBTL 0.02 Syloid MX 309 5 Acematt OK 520 3 Lanco ™ PP 1362 D 2 Modaflow ® 09200 0.5 0.5 0.5 Additol ® CPK 3 3 3 Component II Synt Ex 8 19.2 0 0 Gloss 20° 85.6 81.1 — Gloss 60° 92.9 93.8 18.4 Gloss 85° — — 34 mustard 5 5 5 eosine 2% 5 5 5 coffee 5 5 5 iso-betadine 5 5 5 NH10% 5 5 5 ethanol 50% 5 5 5 N70 black marker 5 4 3

[0190] The data of Table 11 shows that coatings prepared from the dual cure formulation F3 and formulation F11 which is only UV cured had an excellent stain and chemical resistance. Also when adding matting agents in F12 a good stain resistance was maintained.