ONE-PART CURABLE SOFT FEEL COATINGS

Abstract

Disclosed herein arc one part, One-part, curable compositions that have a soft feel when applied as a coating/film and cured, may include a) at least one isocyanurate tri(meth)acrylate or derivative thereof; and at least one of components b)-e), wherein: b) is at least one urethane diacrylate; c) is at least one monofunctional or difunctional reactive diluent; d) is at least one solvent; and e) is additives. The one-part, curable compositions are advantageous with respect to softness and tailorability of softness as well as other properties such as mar resistance, abrasion resistance, stain resistance and chemical resistance. Due to their advantageous properties, embodiments of the one-part, curable compositions described herein are viable for a wide range of coating applications including automotives, aeronautics, cosmetics, small appliances, packaging and consumer electronics. Methods of making and using the one-part, curable are also described herein.

Claims

1. A one-part, curable composition comprising: a) at least one isocyanurate tri(meth)acrylate or derivative thereof and at least one of: b) at least one urethane diacrylate; c) at least one monofunctional or difunctional reactive diluent, different from b) d) at least one solvent; and e) additives.

2. The one-part, curable composition of claim 1, wherein the composition comprises the b) at least one urethane diacrylate.

3. The one-part, curable composition of claim 1, wherein the a) at least one isocyanurate tri(meth)acrylate or derivative thereof comprises tris(2-hydroxyethyl)isocyanurate triacrylate.

4. The one-part, curable composition of claim 1, wherein the composition comprises the d) at least one solvent.

5. The one-part, curable composition of claim 1, wherein the composition comprises the e) additives, wherein the additives are selected from the group consisting of photo-initiators, thermal free radical initiators, accelerators, tri- or higher functionality monomers, polymer waxes or beads, leveling agents, wetting agents, matting agents, colorants, dyes, pigments, slip agents, adhesion promoters, fillers, rheology modifiers, thixotropic agents, plasticizers, UV absorbers, UV stabilizing agents, dispersants, antioxidants, antistatic agents, lubricants, opacifying agents, anti-foam agents, rheology agents and combinations thereof.

6. The one-part, curable composition of claim 5, wherein the e) additives are selected from the group consisting of photo-initiators, thermal free-radical initiators, polymer waxes or beads, accelerators, matting agents, wetting agents, dispersants, leveling agents and combinations thereof.

7. The one-part, curable composition of claim 1, wherein the composition is curable by radiation, by exposure to chemicals, heat or combinations thereof.

8. The one-part, curable composition of claim 1, wherein the a) at least one isocyanurate tri(meth)acrylate or derivative thereof is present in the composition from about 5% to about 80% by weight based on components a), b), c) and e).

9. The one-part, curable composition of claim 1, wherein the a) at least one isocyanurate tri(meth)acrylate or derivative thereof has a molecular weight of less than about 10000 g/mol.

10. The one-part, curable composition of claim 1, comprising: the a) at least one isocyanurate tri(meth)acrylate or derivative thereof; the b) at least one urethane diacrylate; optionally, the c) at least one monofunctional or difunctional reactive diluent; the d) at least one solvent; and the e) at least one additive, wherein the at least one additive is selected from the group consisting of photo-initiators, free-radical initiators, accelerators, matting agents, wetting agents, dispersants, leveling agents and combinations thereof.

11. A one-part, curable composition comprising: a) at least one isocyanurate tri(meth)acrylate or derivative thereof; b) optionally, at least one urethane diacrylate; c) optionally, at least one monofunctional or difunctional reactive diluent; d) optionally, at least one solvent; and e) optionally, additives.

12. A one-part, curable composition consisting of: a) at least one isocyanurate tri(meth)acrylate or derivative thereof; b) at least one urethane diacrylate; d) at least one solvent; and e) at least one photo-initiator as additive.

13. The one-part, curable composition of claim 1, wherein: the a) at least one isocyanurate tri(meth)acrylate or derivative thereof is represented by the formula: ##STR00005## wherein R is H or Me; and X is an alkylene chain (CH.sub.2).sub.n wherein n=2-10 or X is an alkylene group further modified by alkoxylation with ethylene oxide or propylene oxide or a combination thereof or X is an alkylene chain further modified by addition of caprolactone or lactide or a combination thereof; or the a) at least one isocyanurate tri(meth)acrylate or derivative thereof is represented by the formula: ##STR00006## wherein R is H or Me; and Y is a branched or linear alkylene group of 2 to 4 carbon atoms or Y is a branched or linear alkylene group alkoxylated or caprolactone modified alkylene group further modified by alkoxylation with ethylene oxide or propylene oxide or a combination thereof or Y is an alkylene chain further modified by addition of caprolactone or lactide or a combination thereof.

14. The one-part, curable composition of claim 13, wherein Y is selected from the group consisting of CH.sub.2CH.sub.2, CH.sub.2CH(CH.sub.3), CH.sub.2CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2CH.sub.2, alkyl-(OC.sub.2H.sub.4).sub.n, alkyl-(OC.sub.2H.sub.3(CH.sub.3)).sub.n, alkyl-[(OC.sub.2H.sub.4).sub.x(OC.sub.2H.sub.3(CH.sub.3)).sub.y].sub.n, alkyl-(OC(O)C.sub.5H.sub.10).sub.n, alkyl-(OC(O)CH(CH.sub.3)OC(O)CH(CH.sub.3)).sub.n, alkyl-[(OC(O)C.sub.5H.sub.10).sub.x(OC(O)CH(CH.sub.3)OC(O)CH(CH.sub.3)).sub.y].sub.n and combinations thereof.

15. The one-part, curable composition of claim 1, wherein the a) at least one isocyanurate tri(meth)acrylate or derivative thereof is tri s(2-hydroxyethyl) isocyanurate triacrylate.

16. The one-part, curable composition of claim 1, wherein the composition comprises the c) at least one monofunctional or difunctional reactive diluent, the said reactive diluent being selected from the group consisting of 1,3-butylene glycol di(meth)acrylate, butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, alkoxylated hexanediol di-(meth)acrylate, alkoxylated neopentyl glycol di(meth)acrylate, dodecyl di(meth)acrylate cyclohexane dimethanol di(meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, acrylate, ethoxylated bi sphenol A di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, propoxylated neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate tripropylene glycol di(meth)-acrylate, 2-(2-ethoxyethoxy) ethyl (meth)acrylate, 2-phenoxyethyl(meth)acrylate, 3,3,5 -trimethylcyclohexyl(meth)acrylate, alkoxylated lauryl (meth)acrylate, alkoxylated phenol (meth)acrylate, alkoxylated tetrahydrofurfuryl (meth)acrylate, caprolactone (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, dicyclopentadienyl (meth)acrylate, diethylene glycol methyl ether (meth)acrylate, ethoxylated nonyl phenol acrylate, isobornyl (meth)acrylate, isodecyl (meth)acrylate, isooctyl (meth) acrylate, lauryl (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, octyldecyl (meth)acrylate, stearyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, tridecyl methacrylate and/or triethylene glycol ethyl ether methacrylate, t-butyl cyclohexyl (meth)acrylate, alkoxylated nonylphenol (meth)acrylate, phenoxyethanol (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, tetradecyl (meth)acrylate, tridecyl (meth)acrylate, cetyl (meth)acrylate, hexadecyl (meth)acrylate, behenyl (meth)acrylate, diethylene glycol ethyl ether (meth)acrylate, diethylene glycol butyl ether (meth)acrylate, triethylene glycol methyl ether (meth)acrylate, dodecanediol di-(meth)acrylate, acrylated tert-decanoic acid glycidyl ester, acrylated phenyl glycidyl ether, acrylated C.sub.12/C.sub.14 glycidyl ether, poly(tetramethylene) ether glycol diacrylate and combinations thereof.

17. The one-part, curable composition of claims 1, wherein the composition has a viscosity at room temperature (25 C.) of less than 4000 cPs (mPa.Math.s).

18. The one-part, curable composition of any of claim 1, wherein the at least one solvent is selected from the group consisting of methyl ethyl ketone, butyl acetate and combinations thereof.

19. A method of coating a substrate comprising: applying the one-part, curable composition of claim 1, to a substrate; and curing the resulting substrate.

20. The method of claim 19, wherein the curing step comprises curing by exposure to visible radiation, to UV radiation, to LED radiation, to electron-beam radiation or by exposure to chemicals.

21. The method of claim 19, wherein the applying comprises applying to a substrate by spraying, by knife coating, by roller coating, by casting, by drum coating, by dipping and combinations thereof.

22. The method of claim 19, wherein the substrate is selected from the group consisting of steel or other metals, paper, cardboard, glass, thermoplastics, composites, wood, leather and combinations thereof.

23. A method of preparing a coating and/or a film comprising using the one-part, curable composition of claim 1.

24. The method of claim 23, wherein the coating and/or film is for a soft feel or a soft touch coating and/or film.

25. The method of claim 23, wherein said coating and/or film is for automotives, aeronautics, cosmetics, small appliances, packaging and/or consumer electronics.

26. A cured composition resulting from curing the one-part, curable composition of claim 1.

27. The cured composition of claim 26, wherein the cured composition is a coating or film.

28. A cured article comprising the cured composition of claim 26.

29. The cured composition of claim 27, wherein the coating or film is a soft feel or soft touch coating or film.

Description

EXAMPLES

[0067] The Examples using the one-part, curable compositions described herein report properties related to feel, hardness, adhesion, abrasion resistance, stain resistance and mar resistance. The properties reported for the Examples were determined using a number of known techniques. Pencil hardness were determined in accordance with ASTM D3363-05. Adhesion was determined in accordance with ASTM D3359-09. Abrasion resistance was determined in accordance with ASTM F2357-10. MEK (mar) resistance was determined in accordance with ASTM D5402-06. Stain resistance was determined in accordance with ANSI/KCMA A161.1 chemical resistance test with E measurements. Stain resistance was also determined in accordance with General Motors sunscreen and insect repellant resistance test procedures, e.g., GMW14445.

[0068] Molecular weights were determined by gel permeation chromatography (GPC) in THF using polystyrene calibration standards. Samples were run on an Agilent 1100 Series GPC equipped with HP PLGel GPC columns and a Hewlett-Packard 1047A refractive index detector. Results were recorded by Agilent HPLC Chemstation and analyzed with Polymer Laboratories GPC software. Viscosities were measured with a Brookfield viscometer, model DV-II, at 25 C. using a 27 spindle and speed was varied depending on viscosity, typically between 50 and 200 rpm. For each of the Examples, the compositions were applied on standard ABS panels with a target thickness of 36 m. The solvent was flashed off at 60 C./15 minutes. The coatings were cured 150 feet per minute (15.24 m/min) using two Mercury vapor 400W lamps. The ABS panels exhibited a soft feel, characterized as silky, velvety or rubbery, good adhesion on ABS (66 crosshatch) and good resistance to solvent. The coatings of the Examples were compared to commercially available two-part urethane soft feel coatings and were rated by experienced observers on type of feel (rubbery, velvety, silky) and softness (1=no soft feel, 5=best soft feel).

[0069] The compositions of Examples 1-4 are listed below in Table 1, whereby ingredients and weight information are provided for Examples 1-4. It is noted that Table 1 is directed to oligomer diacrylates for the b) at least one urethane diacrylate.

TABLE-US-00001 TABLE 1 Ingredients for one-part, curable compositions Com- Silky 1 Silky 2 Velvety 1 Rubbery po- (Exam- (Exam- (Exam- (Exam- nent Product ple 1) ple 2) ple 3) ple 4) a isocyanurate 16 g 16 g 10 g 7 g tri(meth)acrylate b Aromatic poly- 24 g 12 g 15 g 16.5 g ester urethane diacrylate b aliphatic poly- 0 g 12 g 15 g 16.5 g ether urethane diacrylate e amorphous, 3.4 g 3.4 g 3.4 g 3.4 g fumed silica e Disperbyk 0.35 g 0.35 g 0.35 g 0.35 g 2008 (structured acrylic copolymer dispersant) e 2-hydroxy-2- 2.0 g 2.0 g 2.0 g 2.0 g methyl-1-phenyl- 1-propanone d 50:50 methyl 57.2 g 57.2 g 57.2 g 57.2 g ethyl ketone:butyl acetate

[0070] The compositions of Example 5 are listed below in Table 2, whereby ingredients and weight information is provided for Example 5. It is noted that Table 2 is directed to monomeric diacrylates for the b) at least one urethane diacrylate. ABS panels with the one-part, curable composition of Example 5 were prepared in a similar manner to the ABS panels with the one-part, curable composition of Examples 1-4.

TABLE-US-00002 TABLE 2 Ingredients for one-part, curable compositions Component Product Velvety 2 (Example 5) a reaction product of 1,6-hexane 24 g diisocyanate trimer with an hydroxyl acrylate b alkoxylated phenol acrylate 14 g b 2PO neopentyl glycol 4 g diacrylate e amorphous, fumed silica 3.4 g e Disperbyk 2008 (structured 0.35 g acrylic copolymer dispersant) e 2-hydroxy-2-methyl-1-phenyl- 2.0 g 1-propanone d 50:50 methyl ethyl ketone:butyl 57.2 g acetate

[0071] A comparative Example is also provided and is directed to a two-part system comprising isocyanate and a difunctional polyol in solvent or water. The comparative Example employed 87.45 g of ST2010 clear resin (available from The Alsa Corporation) with 22.05 g of ST2010 hardener (also available from The Also Corporation). ABS panels with the two-part, curable composition of the comparative Example were prepared in a similar manner to the ABS panels with the one-part, curable composition of Examples 1-5.

[0072] Table 3 is provided below and includes test results for Examples 1-5 and the comparative Example with respect to certain properties, such as feel, pencil hardness, adhesion and abrasion resistance.

TABLE-US-00003 TABLE 3 Properties of Examples 1-5 and the Comparative Example Overall feel Pencil Adhe- Abrasion Feel (5 = best) Hardness sion Resistance Silky 1 (Ex. 1) silky 4 H 100 300 Velvety 1 velvety 4 B 100 69 (Ex. 3) Silky 2 (Ex. 2) silky 4 F 100 221 Rubbery (Ex. 4) rubbery 3.5 B 100 65 Velvety 2 velvety 4.5 B 100 32 (Ex. 5) Comparative rubbery 5 <9B 100 43 Example

[0073] Table 4 is provided below and includes test results for Examples 1-5 and the comparative Example with respect to stain resistance to multiple products and mar (MEK) resistance.

TABLE-US-00004 TABLE 4 Properties of Examples 1-5 and the Comparative Example Stain Stain Stain Stain MEK Resis- Resis- Resis- Resis- Resis- tance to tance to tance to tance to tance Coffee Mustard Ketchup Red Wine (double (E) (E) (E) (E) rubs) Silky 1 (Ex. 1) 9.52 17.29 2.23 12.71 200+ Velvety 1 (Ex. 3) 13.95 17.89 4.59 22.5 67 Silky 2 (Ex. 2) 13.46 15.79 2.91 17.66 167 Rubbery (Ex. 4) 9.99 18.63 2.67 16.38 40 Velvety 2 (Ex. 5) 16.87 14.82 4.37 16.09 171 Comparative Example 16.78 20.11 5.64 21.79 15

[0074] Table 5 is provided below and includes test results for Examples 1-5 and the comparative Example with respect to material resistance to multiple products.

TABLE-US-00005 TABLE 5 Properties of Examples 1-5 and the Comparative Example Material Resistance Material Resistance to To Sunscreen Rating Insect Repellant Rating Silky 1 (Ex. 1) 2 2 Velvety 1 (Ex. 3) 2 2 Silky 2 (Ex. 2) 2 2 Rubbery (Ex. 4) 2 2 Velvety 2 (Ex. 5) 2 1.5 Comparative Example 2 2

[0075] As can be seen from Tables 3-5, the one-part, curable compositions described herein perform better in the areas tested when compared to conventional two-part compositions.

[0076] The one-part, curable compositions described herein are preferably deposited on a substrate by spraying. The one-part, curable compositions described herein may be formulated to yield a solvent resistant coating with a variety of touch sensations from rubbery to silky by varying the amount of component a).

[0077] When the word about is used in this specification in connection with a numerical value, it is intended that the associated numerical value include a tolerance of 10% around the stated numerical value. Moreover, when reference is made to percentages in this specification, it is intended that those percentages are based on weight, i.e., weight percentages.

[0078] It will now be apparent that new, improved and nonobvious compositions have been described in this specification with sufficient particularity as to be understood by one of ordinary skill in the art. Moreover, it will be apparent to those skilled in the art that modifications, variations, substitutions and equivalents exist for features of the compositions which do not materially depart from the spirit and scope of the embodiments disclosed herein. Accordingly, it is expressly intended that all such modifications, variations, substitutions and equivalents which fall within the spirit and scope of the invention as defined by the appended claims shall be embraced by the appended claims.

[0079] Within this specification embodiments have been described in a way which enables a clear and concise specification to be written, but it is intended and will be appreciated that embodiments may be variously combined or separated without parting from the invention. For example, it will be appreciated that all preferred features described herein are applicable to all aspects of the invention described herein.