High temperature resistance, radiation curable maskant for metal substrates |
|||||||
| 申请号 | EP14182406.0 | 申请日 | 2014-08-27 | 公开(公告)号 | EP2848656B1 | 公开(公告)日 | 2017-03-22 |
| 申请人 | DYMAX CORPORATION; | 发明人 | Nebioglu, Ahmet; Morin, Michael A.; Cayer, Christopher Alan; Rahim, Marufur; | ||||
| 摘要 | |||||||
| 权利要求 | |||||||
| 说明书全文 | This invention relates to temporary maskants curable by actinic radiation for use in protecting metal substrates during grit blasting and plasma spray processing. The invention relates to a formulation capable of polymerization through exposure to actinic radiation that can be used to protect a metal substrate from high temperature and abrasive processing. These find use in the manufacture of such products as turbine blades, engine parts, circuit boards, one glass solution (OGS) and orthopedic replacement joints. The use of temporary radiation-curable masks in the processing of metal surfaces is well known. In many masking applications, two-part, solvent based or thermally cured maskants are impractical and uneconomical. Radiation curable masks can be applied easily and cured quickly using actinic radiation. The invention provides a method for shielding a metal substrate surface during the application of heat to the surroundings of the substrate which comprises:
The invention also provides a liquid maskant composition which comprises
Methods claims 1 to 13 and liquid maskant composition claim 14 define the invention. Generally, the composition of the liquid maskant composition comprises a polycarbonate caprolactone urethane (meth)acrylate oligomer, a polymerizable diluent, a photoinitiator, an optional thickening agent, and optional other additives. Examples of suitable polycarbonate caprolactone urethane diacrylate oligomer, or a polycarbonate caprolactone urethane dimethacrylate oligomers have the formula wherein:
In a preferred embodiment in each of the above formulas, k ranges from 3 to 20, more preferably from 5 to 15. In a preferred embodiment in each of the above formulas, n ranges from 2 to 15, more preferably from 3 to 10. In a preferred embodiment in each of the above formulas, m ranges from 2 to 15, more preferably from 3 to 10. The polyurethane (meth)acrylate oligomer is the reaction product of a polycarbonate caprolactone polyol containing two or more hydroxyl groups; an aliphatic diisocyanate with a molecular weight of from 200 to 500 such that there is an equivalent weight ratio of isocyanate to polyol of from 1.5-2.5 to 1.0. The reaction is terminated using a saturated and/or unsaturated monofunctional alcohol with a molecular weight of from 40 to 500. Examples of suitable polycarbonate polyols are reaction products of diols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 hexanediol, neopentyl glycol, 2-methyl-1,3-pentanediol, 1-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol and 3-methyl-1,5-pentanediol or mixtures thereof with phosgene or dialkylcarbonates or diarylcarbonates or cyclic carbonates. Typical molecular weight of the polycarbonate polyols used in the present invention are from 300 (4,98e-25 kg) Daltons, and preferably from 1000 (1,66e-24 kg) to 3000 (4,98e-24 kg)Daltons. Examples of suitable polycarbonate caprolactone polyols are the reaction products of the polycarbonate polyols mentioned above and 2-oxepanone. Typical molecular weight of the polycarbonate caprolactone polyols used in the present invention are from 500 (8,3e-25 kg) to 5000 (8,3e-24 kg) Daltons and preferably from 1000 to 3000 Daltons. Examples of suitable diisocyanates are hexamethylene diisocyanate (HDI), trimethyl hexamethylene diisocyanate, bis(4-isocyanatocyclohexyl)methane (H12MDI), isophorone diisoycanate (IPDI), tetramethylxylene diisocyanate (TMXDI), trimethylhexamethylene diisocyanate (TMDI), toluene diisocyanate (TDI). Non-exclusive examples of suitable capping agents are: 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate. N-(2-Hydroxypropyl)methacrylamide and pentaerythritol triacrylate. Optionally chain extender diols may be used to increase molecular weight of polyurethane (meth)acrylate. Non-exclusive examples of chain extenders, but are not limited to, are ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 hexanediol, neopentyl glycol, 2-methyl-1,3-pentanediol, 1-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol and 3-methyl-1,5-pentanediol or combinations thereof. Optionally a catalyst may be used to make polyurethane (meth)acrylate. Examples of suitable catalysts are: tin catalysts such as; dibutyltin dilaurade, stannous octoate, dibutyltin diacetate, bismuth catalysts, and zinc octoate. A suggested reaction of urethane (meth)acrylate oligomer is as follows. Polyol of OH-functionality 2 or 3, is blended with an excess of polyisocyanate of NCO-functionality 2 or 3 in the equivalent weight ratio of isocyanate to polyol between 1.5-2.5 to 1.0. A reaction vessel with polyol and polyisocyanate is themostatted at a temperature of from 20°C to 100° C, or, preferably from 30° C. to 80° C, or more preferably from 60° C. to 70° C. A catalyst may be added in the concentrations of from 10 to 1000 ppm, or, preferably from 20 to 700 ppm, or more preferably from 50 to 100 ppm. Typical reaction time is 65° C. with a concentration of catalyst 100 ppm is from 3 to 4 hours. An increase (decrease) of the temperature leads to acceleration (deceleration) of a reaction of urethane prepolymer formation. Upon completion of a reaction indicated by termination of disappearance of NCO characteristic absorption in the IR spectrum, a capping agent, that is a hydroxyl substituted acrylate or methacrylate is added to the mixture which has residual non-reacted NCO. Upon completion of a capping reaction indicated by complete disappearance of NCO characteristic absorption in the IR spectrum the final urethane (meth)acrylate is formed. Typical reaction time at 65° C. with a concentration of catalyst 100 ppm is from 8 to 10 hours. A concentration of a capping agent is selected the way that a number of OH-equivalents of the capping agent is equal to a number of residual non-reacted NCO. The liquid maskant composition is formed by mixing the ingredient components. Suitable examples of the reactive, i.e. polymerizable diluent may be any substituted vinyl monomer with one or more functional groups. Such materials as 2-hydroxyethyl (meth)acrylate, isobornyl (meth)acrylate, n-vinyl caprolactam, n,n-dimethyl acrylamide, and materials of similar compositions that are known to those skilled in the art and mixtures thereof. The photoinitiator is of any class of free radical photoinitiators, including Norrish Type I and Type II photoinitiators. Examples of suitable Type I homolytic free-radical photoinitiators are benzoin derivatives, methylolbenzoin and 4-benzoyl-1,3-dioxolane derivatives, benzilketals, α,α-dialkoxyacetophenones, α-hydroxy alkylphenones, α-aminoalkylphenones, acylphosphine oxides, bisacylphosphine oxides, acylphosphine sulphides, and halogenated acetophenone derivatives. Examples of suitable Type-II (hydrogen abstraction) photoinitiators are aromatic ketones such as benzophenone, xanthone, derivatives of benzophenone (e.g. chlorobenzophenone), blends of benzophenone and benzophenone derivatives (e.g. Photocure 81, a 50/50 blend of 4-methyl-benzophenone and benzophenone), Michler's Ketone, Ethyl Michler's Ketone, thioxanthone and other xanthone derivatives like Quantacure ITX (isopropyl thioxanthone), benzil, anthraquinones (e.g. 2-ethyl anthraquinone), and coumarin. Chemical derivatives and combinations thereof may also be used. The thickening agent may be of any thixotrope known to those who are skilled in the art. These include untreated fumed silica, surface modified fumed silica, polyamide thixatropes, and mixed mineral thixotropes. The maskant composition may also include additional additives, such as heat stabilizers, UV-light stabilizers, free-radical scavengers (e.g., hindered amine light stabilizer compounds), dyes, pigments, surfactants, plasticizers, opacity-modifying agents, and combinations thereof. The composition may also contain additional ingredients, that is overall liquid maskant composition includes the urethane (meth)acrylate oligomer, a polymerizable diluent, a photoinitiator, an optional thickening agent, and optional other additives. In the overall liquid maskant composition the polycarbonate caprolactone urethane (meth)acrylate oligomer is usually present in an amount of from 15% by weight to 85% by weight, preferably from 30% by weight to 70% by weight, and more preferably from 40% by weight to 60% by weight. In the overall liquid maskant composition the reactive diluent is usually present in an amount of from 20% by weight to 60% by weight, preferably from 20% by weight to 50% by weight, and more preferably from 25% by weight to 40% by weight. In the overall liquid maskant composition the photoinitiator is usually present in an amount of from 1% by weight to 10% by weight, preferably from 2% by weight to 7% by weight, and more preferably from 3% by weight to 5% by weight. In the overall liquid maskant composition the thickener may be present in an amount of from 0% by weight to 15% by weight, preferably from 2% by weight to 10% by weight, and more preferably from 2% by weight to 6% by weight. In the overall liquid maskant composition the optional additional additives may be present in an amount of from 0% by weight to 5% by weight, preferably from 0.01% by weight to 4% by weight, and more preferably from 0.05% by weight to 3% by weight. In use, the liquid maskant composition is applying the maskant composition onto a surface of a substrate, such as a metal substrate. The liquid maskant composition is then cured by exposing to sufficient actinic radiation to polymerize or crosslink the composition into a dried maskant. Polymerization may be initiated by exposure to ultraviolet and/or visible light. The length of time for exposure is easily determined by those skilled in the art and depends on the selection of the particular components of the radiation curable composition. Typically exposure ranges from 0.2 second to 120 seconds, preferably from 0.5 seconds to 60 seconds, and more preferably from 0.5 seconds to 30 seconds. Typical exposure intensities range from 5 mW/cm2 to 2500 mW/cm2, preferably from 50 mW/cm2 to 1500 mW/cm2, and more preferably from 100 mW/cm2 to 1000 mW/cm2. In one embodiment, the liquid maskant composition is applied to a substrate surface at a thickness of from 0.005 inch (0,000127 m) to 0.060 inch (0,001524 m). In another embodiment the film thickness has a thickness of from 0.005 inch (0,000127 m) to 0.040 inch (0,001016 m). The masked substrate may then by used in typical applications, for example in the production of aircraft parts, medical orthopedics, automotive parts, agricultural parts, or the like, which may require protecting the substrate surface from heating conditions at a temperature of from 400 °F (204,4 °C) to 600 °F (315,6 °C) for a duration of from 20 minutes to 30 minutes. After the processing of the metal surface, the maskant can be removed from the metal surface by peeling or by burning off. The burn off process can be in the range of 500°F (260 °C) to 1,200°F (648,9 °C) for a period of time of a few minutes to several hours, leaving essentially no residue. The following examples serve to illustrate the invention. Samples of the dimensions of films cured under a metal halide lamp at 250 mW/cm2 for 30 sec in a Teflon mold 3"(76mm) long, 0.75"(19mm) wide and 0.04"(1mm) deep. Samples were then placed in an oven at 500 °F (260°C) for 20 minutes, removed and allowed to cool to room temperature. Heat treated and non-heat treated samples were then pulled on an Instron Model 4467 on a 200lb (90,7 kg) load cell at a speed of 1"/min. Tensile at break (psi), elongation at break and Young's modulus (psi) were recorded. Samples were prepared by casting 0.04"(1 mm) thick and 0.87"(22 mm) wide maskants onto a nickel alloy substrate and curing for 30 seconds under a metal halide lamp at 250 mW/cm2. Samples were then placed in an oven at 500 °F (260 °C) for 20 minutes, removed and allowed to cool to room temperature. Heat treated and non-heat treated samples were then pulled at 90° using a Thwing-Albert peel tester (Model FP-2255 with a 10kg load cell) at a speed of 20 mm/sec. Max peel strength (grams) and peel distance (mm) before break recorded. The following inventive Example composition B, and comparative Example compositions C, D and E were formed, where the ingredients are in parts by weight. The inventive polycarbonate caprolactone urethane acrylate oligomers are of the composition described above. The polyester, polyether and polybutadiene are Bomar™ BR-403, BR-543 and BR-641, respectively, available from Dymax Oligomer and Coatings. Each sample was prepared by blending components until mixture was homogenous. The following conditions and results are noted. The polycarbonate caprolactone oligomer retains enough tensile strength (466 psi) (3212956 Pa) and elongation (62%)to be peeled off from the substrate after heating, even though adhesion to the substrate has increased but the higher cohesive strength (3511 psi) (24207492 Pa) still makes the film peelable. The polyester oligomer composition shows a reduction of tensile strength which is 227 psi (1565109 Pa) and it not enough to withstand while being stretched. In addition, the lower modulus of 599 is an indication of weak cohesive strength. As a result the film breaks readily when attempted to be removed. The polyether oligomer composition has weak tensile (128 psi) (882528 Pa) and lower flexibility (12%) which makes it easily breakable during peeling the film. Similar to the polyether oligomer composition, the polybutadiene oligomer composition substantially loses elongation (8%) and along with increases in modulus, consequently makes it very brittle. For this reason, the film cannot be bent 90° without breaking and could not be tested using the peel tester. The polycarbonate and polycarbonate caprolactone oligomers impart enough heat resistance to allow the maskant composition to survive high temperatures for an extended period of time without breaking down. Afterwards, the resultant films can be removed through peeling. Alternatively, the films could be removed by burning them off at temperatures greater than 600°F (316 °C) without leaving any residue as found by TGA analysis (See |
||||||
