US 2010.0022685A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2010/0022685 A1 Buffy et al. (43) Pub. Date: Jan. 28, 2010

(54) RAPID DRY FIBERGLASS STAIN Related U.S. Application Data (75) Inventors: Jarrod J. Buffy, Waterville, OH (60) Provisional application No. 61/083,002, filed on Jul. (US); William V. Pagryzinski, Leo, 23, 2008. IN (US) Publication Classification Correspondence Address: (51) Int. Cl. CALFEE HALTER & GRISWOLD, LLP C09D 5/00 (2006.01) 800 SUPERIORAVENUE, SUITE 1400 (52) U.S. Cl...... 523/400 CLEVELAND, OH 44114 (US) (57) ABSTRACT (73) Assignee: THERMA-TRU CORP., Maumee, A portion of the linseed oil ingredient used in fiberglass OH (US) composite stains is replaced with a modified Cashew Nut Shell Liquid (CNSL) resin. As a result, the drying time of the (21) Appl. No.: 12/505,702 stain is shortened considerably yet is still long enough to allow working of the stain into the composite for developing (22) Filed: Jul. 20, 2009 a simulated wood appearance. US 2010/0022685 A1 Jan. 28, 2010

RAPID DRY FIBERGLASS STAN 0007 Accordingly, this invention provides a new stain for fiberglass composite Substrates comprising a colorant and a resin-forming component, the resin-forming component 0001. This application claims the benefit of U.S. Provi comprising a linseed oil ingredient and a modified CNSL sional patent application Ser. No. 61/083,002 filed on Jul. 23, CS1. 2008, for RAPID DRY FIBERGLASS STAIN, the entire disclosure of which is fully incorporated herein by reference. DETAILED DESCRIPTION Fiberglass Composite BACKGROUND 0008. This invention is directed to making stains for fiber 0002. In order to make fiberglass products such as fiber glass composites (or simply “fiberglass'), i.e., shaped articles glass doors look like they are made from wood, the fiberglass formed from glass fibers embedded in a thermoplastic or composite (i.e., the fiberglass/polymer binder mass) is col thermosetting resin, especially high quality exterior door sys ored with a suitable stain. Such stains are typically composed tems made from Such composites. of various colorants and an organic solvent such as mineral 0009 High quality fiberglass exterior doors are typically spirits. Drying oils, which are liquid fatty acids capable of made by compression molding, thereby producing simulated hardening to tough, Solid films when exposed to air, are also wooden doors bearing molded surface skins exhibiting a normally included. A siccative, which is a metal salt of a short wood grain Surface texture. A Suitable stain is then applied chain organic acid (e.g., cobalt di-(2-ethylhexanoate)) is also and worked into the surface by hand, typically for several normally included to cause the drying oil to cure, thereby minutes to an hour or more, thereby producing a finished forming a resinous binder for the colorant. Additional con surface having the look and feel of natural wood. Under ventional ingredients may also be included. production conditions where skilled workers, Sophisticated 0003. The most commonly used drying oil used for this spray equipment, drying ovens and the like are available, purpose is linseed oil, which typically contains ~58% C-lino finishes almost indistinguishable from natural wood can be lenic acid, ~14% linoleic acid, ~19% oleic acid, ~4% steric obtained. acid and ~5% palmitic acid. In some cases, the linseed oil is 0010. Once dry, the stained surface skins are typically prepolymerized (“modified') into a liquid resinous products covered with one or more protective coatings or “topcoats.” before being used. For example, the linseed oil can be heated These can be formed from a variety of different polymer at elevated temperature, thereby producing “heat-bodied lin resins Supplied in any convenient form such as organic solu seed oil. Alternatively, the linseed oil can be co-polymerized tions, aqueous dispersions and molten. See, for example, the with another monomer Such as dicyclopentadiene. See, for above-noted U.S. Pat. No. 6,358,614, as well as U.S. Pat. No. example, U.S. Pat. No. 5.288.805 and U.S. Pat. No. 6,358, 6,210,057 and U.S. Pat. No. 6,979,475, the disclosures of 614, the disclosures of which are incorporated herein by which are also incorporated herein by reference. reference. 0011. The inventive fiberglass stains are compatible with 0004 Stains made with drying oils based on linseed oil, all such fiberglass composites and topcoats. That is to say, the whether modified or unmodified, can take two to three days to inventive fiberglass stains are generally useful for staining cure when applied to fiberglass composites, since Such com fiberglass composites made from all materials which are now posites do not absorb stains like natural wood. This represents known, or which become known, as useful for making fiber a significant problem in practice because of the delay glass composites. Similarly, all of the protective coatings involved before the stain can be overcoated with another coat which are now known, or which become known, for overcoat of stain and/or a protective clear coat Such as polyurethane or ing fiberglass stains can be used to top coat the fiberglass the like. stains of this invention. 0005 Recently, Palmer International of Shippack, Pa., introduced a line of proprietary modified (prepolymerized) Colorant drying oil resins based on Cashew Nut Shell Liquid (CNSL). 0012. The inventive stains, like other conventional fiber Although these liquid resinous products are said to provide glass stains, include Suitable colorants to develop the neces low-VOC, air-drying wood stains capable of drying in as little sary colored appearance. Although dyes can be used, pig as 4 to 5 hours, they dry too quickly to allow sufficient time for ments (tint pastes) are the colorants of choice. Examples working these stains into fiberglass composite Substrates, include rhodamine red (pigment red 81), carbazole violet which is necessary when high quality, wood-simulating fiber (pigment violet 23), metallized azo reds (such as calcium glass doors are being made. Moreover, the adhesion of stains lithol, lithol rubine), diarylide yellows (Yellow 14), made with these products to fiberglass composite Substrates is monoarylide yellow (Yellow 74), naphthol reds (e.g., Red 22, inadequate to be commercially viable. 122, 2), phthalocyanine blue (blue 15:3 et al.), phthalocya nine green (Green 7), quinacridone red (Red 122), oranges SUMMARY (Orange 5 and 16), methyl violet (Violet 3), and carbon black (both acidic and neutral grades). Further examples include 0006. In accordance with this invention it has been found AL 509 Burnt Umber tint paste AL 505 Burnt Sienna tint that the drying time of a fiberglass stain can be shortened to paste AL 611 Red Oxide tint paste and AL 329 Black tint just 4 or 5 hours without Substantially compromising the paste, just to name a few. Generally speaking any colorant working time needed for working the stain into a fiberglass which is now known, or which becomes known, as useful in composite Substrate, or the adhesion of the applied stain making fiberglass stains can be used as the colorant in the coating to this Substrate, by replacing a portion of the linseed fiberglass stains of this invention. oil ingredient normally used in Such fiberglass stains with 0013 Because the inventive stains are formulated, in part, such a modified CNSL resin. with a modified CNSL, less solvent and hence more colorant US 2010/0022685 A1 Jan. 28, 2010

can be used relative to conventional fiberglass stains. There modified by known techniques for improving its performance fore, colorant loadings in the inventive stains will typically be as an air drying oil in coating formulations. For example, on the order of about 25 to 65 wt.%, more commonly about unmodified linseed oil can be heated at elevated temperatures 35 to 55 wt.%, and even about 42 to 48 wt.%. for a suitable time to develop a “heat-bodied” linseed oil. Alternatively or additionally, unmodified linseed oil can be Solvent co-polymerized with another monomer Such as dicyclopen 0014. The inventive stains, like other conventional fiber tadiene as shown, for example, in the above-noted U.S. Pat. glass stains, also include Suitable solvents which basically act No. 5,288,805 and U.S. Pat. No. 6,358,614, the disclosures of as liquid carriers. Examples include mineral spirits, naphthas, which are incorporated herein by reference, which are Xylenes, toluenes, trimethyl benzenes, ethyl toluenes and believed to describe the DILULINTM line of linseed oil/dicy ethylbenzenes and mixtures thereof. Mineral spirits are nor clopentadiene copolymers available from Cargill, Inc. of mally be used. Minneapolis, Minn. 0.015. As indicated above, less solvent is used in the inven 0020. In accordance with this invention, the resin-forming tive fiberglass stains relative to conventional stains, because a component of the inventive stain is formed in significant part significant part of its resin-forming component is composed from a modified CNSL resin. For this purpose, the modified of a modified CNSL. Thus, the amount of solvents in the CNSL can be an ethoxylated phenol of the type described in inventive stains (including any solvent that may be present in U.S. Pat. No. 7,084,103, which recently issued to Palmer the resin-forming component, as Supplied from the manufac International, Inc. of Shippack, Pa., the disclosure of which is turer) is typically on the order of about 4 to 30 wt.%, more incorporated herein by reference. As described in that patent, typically 5 to 20 wt.%, and even about 6 to 15 wt.%, based Cashew Nut Shell Liquid (CNSL) is composed predomi on the weight of the stain as a whole. Because of this relatively nantly of anacardic acid, which, when treated in the presence low concentration of organic solvents, the inventive fiberglass of heat, is decarboxylated giving rise to a meta-substituted stains typically exhibit a solids content of -70 wt.%, -80 wt. phenol, 3-pentadecenyl phenol compound (trivial name: car % or even -85 wt.% or more and VOC contents of -300 g/1 danol). The related phenol, 5-pentadecadienyl resorcinol, or less, ~250 g/l or less, and even ~200 g/l or less. may also be present in CNSL (trivial name: cardol). When 0016. In some embodiments of the invention, approxi this material is contacted with ethylene oxide, normally in the mately 10 to 30 wt.%, more typically about 15 to 25 wt.%. presence of a Suitable catalyst Such as a Lewis acid oralkaline based on combined weight of all the solvents, are slowly metal hydroxide, a highly ethoxylated product is obtained. evaporating solvents commonly known as “tail solvents.” The When dissolved in a suitable solvent, this product provides a remainder of the solvents in these embodiments exhibit fast to low-color, high solids/low-VOC, low viscosity fast drying air moderate evaporation, such as mineral spirits, naphtha, Sol dry resin System capable of producing film coatings with vent 142 petroleum distillate, and the like. It is preferred to excellent hardness. use combinations of these faster evaporating solvents such 0021 Products made under this patent are believed to be that the solvents flash off at different intervals. In these the Cashew thaneTM line of resins marketed by Palmer Inter embodiments, the majority of solvent, i.e., >50%, should national, with Cashew thane AC5680, Cashew thane 1630-01 flash off within a period of from 2 to 10 minutes. Most and Cashew thane 1612-75MS being especially interesting. In preferably, solvent 142 petroleum distillate, mineral spirits, general, these products can be described as low color, highly and tridecyl alcohol tail solvent are employed. unsaturated CNSL modified phenolic resins in mineral spirits having high solids contents (e.g., 55-85%. 70-80%, or even Other Additives -75%) and VOC contents of -300 g/l or less. 0022. Another type of modified CNSL resin that can be 0017. The inventive stains may also contain other known used to make the resin-forming component of the inventive additives inconventional amounts. For example, the inventive stain are the melamine modified cashew nut oils described in stains can include leveling agents, drying agents, e.g., metal U.S. Pat. No. 7,084,103, which also recently issued to Palmer naphthenates such as cobalt naphthenate, calcium naphthen International, Inc., the disclosure of which is also incorpo ate and magnesium naphthenate, ultraviolet absorbers pref rated herein by reference. As described there, melamine ring erably of the non-sacrificial type, e.g., hindered amine stabi containing copolymers made by reacting a melamine base lizers such as TINUVINTM 292 and TINUVINTM 328, wax, resin with Cashew Nut Shell Liquid (CNSL) are also capable thickeners such as various clay minerals, anti-skin agents, and of producing film coatings with excellent hardness from high the like. Solids/low-VOC coating compositions. 0023 Essentially any amount of modified CNSL resin can Resin-Forming Component be included in the resin-forming component of the inventive 0018. In accordance with this invention, the resin-forming stain. For example, concentrations as low as 25, 20, 15, 10 or component of the inventive stain, i.e., the polymers and/or even 5 wt.% and as high as 95 or even 97 or even 98 wt.%. polymer precursors which form a solid, hardened resinous based on the total weight of resin-forming ingredients (i.e., mass once the stain dries and cures, is formed from a combi including all resins and resin precursors but excluding sicca nation of a linseed oil ingredient and a modified CNSL resin. tives and any solvent that may be included in these ingredients As a result, the inventive stain dries slowly enough to allow as supplied from the manufacturer). Normally, however, the the necessary working to be done for developing the desired concentration of this ingredient will be about 50 to 90 wt.%. simulated wood grain appearance (e.g., 1-3 hours) yet fast 60 to 85 wt.% or even 65 to 80 wt.%, based on the weight of enough to be overcoated within 6 hours or so. the entire resin-forming component. 0019. The linseed oil ingredient is preferably formed from 0024. Similarly, the amount of linseed oil ingredient that unmodified linseed oil. Alternatively, it can be formed, can be included in the resin-forming component of the inven wholly or partially, from modified linseed oil which has been tive stain can be as little as 5, 3 or even 2 wt.% or as much as US 2010/0022685 A1 Jan. 28, 2010

75, 80, 85, 90 or even 95 wt.%, based on the weight of the with any convenient applicator Such as a rag, bristle brush, entire resin-forming component. Normally, however, the foam brush, spray applications or any other application tech amount of this ingredient will be about 10 to 50 wt.%, 15 to nique which is or becomes known for applying fiberglass 40 wt.% or even 20 to 35 wt.%. stains to fiberglass Substrates. Then, depending on the nature 0025. In general, the relative amounts of the modified of the substrate being stained and the surface effect desired, CNSL resin and linseed oil ingredient included in particular the stain can simply be allowed to dry undisturbed, or the stain fiberglass stains made in accordance with this invention can be worked into the substrate's surface to develop the should be selected to achieve the desired combination of visual effect sought. drying and working times. So, for example, the particular fiberglass stain described in the following working example, WORKING EXAMPLE which contained ~27 wt.% linseed oil ingredient and -73 wt. % modified CNSL resin based on the combined weights of 0030. In order to more thoroughly describe this invention, resin-forming ingredients in the stain, dried in about 6 hours. the following working example is provided. In this working By increasing the amount modified CNSL resin and decreas example, a fiberglass stain made in accordance with this ing the amount of linseed oil ingredient, the drying time can invention contained the ingredients set forth in the following be shortened and conversely. Thus, a person of ordinary skill Table 1: in the art can easily formulate fiberglass stains having the particular drying times desired by Suitably adjusting the pro TABLE 1 portions of these two ingredients in the stains. Thus, fiber TOTAL glass stains having drying times anywhere between 3 hours to 2 days can easily be produced in accordance with this inven INGREDIENTS FUNCTION GRAMS W9% tion. Thus, fiberglass stains having drying times on the order Cashewthane AC5680 Resin-Former 384.51 38.55% of about 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, 20, 24 hours and even (75 wt.% resin, 25 wt. longer are contemplated. Similarly, producing fiberglass % mineral spirits) Raw Linseed Oil Resin-Former 103.23 10.35% stains having drying times between 3-24 hours, 4-12 hours, CabOSM-5 Thickener 6.68 O.67% and even 5-9 hours is also contemplated. ASP-200 Thickener 41.75 4.19% 0026. In addition to the linseed oil ingredient and a modi AL SO9 BURNTUMBER Tint Paste 95.5 9.57% fied CNSL resin discussed above, the resin-forming compo AL SOS BURNT SIENNA Tint Paste 162.01 16.24% Tint Paste nent of the inventive stains can also include other polymers AL 611A RED OXIDE Tint Paste 166.18 16.66% which are known, or which become known, as additional Tint Paste resin forming ingredients or 'secondary resins' in fiberglass AL 329 BLACK Tint Paste Tint Paste 21.98 2.20% stains and other coatings. Examples include the oil modified 10% Ca CHEM ALL (OMG#21) Siccative 2.88. O.29% 12% Co. CEM-ALL (OMG#109) Siccative 0.72 O.07% urethanes and medium or long oil alkyd polymers described 12% Mn CEEM-ALL Siccative O.71 O.07% in the above-noted U.S. Pat. No. 5,288,805. If so, such sec (OMG#466) ondary resins can be used in amounts as low as 5, 4, 3, 2 or NUXTRA Zir 24% Siccative 1.2 O.12% even 1 wt.% and as high as 30, 40 or even 50 wt.%. , based SKINO #2 (OMG#863) Anti-Skin 1.9 O.19% on the weight of the entire resin-forming component. In some Agent embodiments, the inventive fiberglass stain is free or essen MINERAL SPIRITS Solvent 8.26 O.83% tially free of Such secondary resins. 997.51 1OOOO 0027. As indicated above, less solvent is used in the inven tive fiberglass stains relative to conventional stains, because a significant part of its resin-forming component is composed 0031. This stain was prepared by mixing the two resin formers (raw linseed oil Cashew thane AC 5680) by mechani of a modified CNSL resin. That being the case, the total cal stirring followed by adding, with stirring, the mineral amount of resin forming component in the inventive fiber spirits, thickeners and then the siccatives and anti-skin agent. glass stain (i.e., including all resins and resin precursors but The mixture was stirred until a homogenous mixture was excluding siccatives and any solvent that may be included in obtained, about 20 minutes to 2 hours, thereby producing a these ingredients as Supplied from the manufacturer) will stain “base.” To this stain base, the various tint pastes were normally be about 20 to 60 wt.%, 30 to 50 wt.%, or even 35 then added and stirring continued until the color of the com to 45 wt.%. position was completely uniform and constant. 0032. The stain so-obtained was then applied by means of Method of Manufacture and Use a rag to the upper molded surface skin of a compression 0028. The inventive fiberglass stains can be manufactured molded fiberglass exterior door, the molded skin surface hav and used in a conventional manner. So, for example, the ing a simulated wood grain Surface texture. The applied stain inventive stains can be made by first forming a “stain base' by was then worked into this Surface by moving the stain in a mixing the resin-formers (linseed oil ingredient, modified circular or cross-grain motion to cause the stain to penetrate CNSL and secondary resin, if any) by mechanical stirring the grainy textured surface and then Smoothed in the direction followed by adding, with stirring, the solvent, siccatives and of the grain. Staining and working were done in discrete other additives. The mixture can then be farther stirred until a sections of the doors surface, with the entire job taking about homogenous mixture is obtained, which normally takes about 40 minutes. Six hours after staining and working were com 20 minutes to 2 hours. To the stain base so made is then added pleted, it was determined that the dried stain coating was the particular colorants to be used followed by additional ready to receive a conventional topcoat by the adhesion tape stirring until a uniform and constant color is obtained. test of ASTM-D3359. 0029. The inventive stain can then be used in a conven 0033 Although only a few embodiments of the invention tional manner by applying the stain to a fiberglass Substrate have been described above, it should be appreciated that US 2010/0022685 A1 Jan. 28, 2010

many modifications can be made without departing from the 9. The stain of claim 1, wherein the modified CNSL resin is spirit and scope of the invention. All Such modifications are the reaction product of a melamine base resin and CNSL. intended to be included within the scope of this invention, 10. The stain of claim 1, wherein the modified CNSL resin which is to be limited only by the following claims: is the reaction product of ethylene oxide and CNSL. 1. A stain for fiberglass composites comprising a colorant 11. The stain of claim 10, wherein the stain has a solids and a resin-forming component, the resin-forming compo content of at least about -70 wt.% and a VOC content of -300 nent comprising a linseed oil ingredient and a modified CNSL g/l or less. CS1. 12. The stain of claim 11, wherein the stain contains about 2. The stain of claim 1, wherein the linseed oil ingredient is 50 to 90 wt.% of modified CNSL resin and about 10 to 50 wt. unmodified linseed oil. % linseed oil ingredient, based on the weight of the resin 3. The stain of claim 2, wherein the modified CNSL resin is forming component. the reaction product of ethylene oxide and CNSL. 4. The stain of claim 3, wherein the stain has a solids 13. The stain of claim 12, wherein the stain contains 20 to content of at least about ~70 wt.% and a VOC content of -300 40 wt.% of a secondary resin, based on the weight of the g/l or less. resin-forming component, the secondary resin comprising an 5. The stain of claim 4, wherein the stain contains about 50 oil modified urethane, a medium oil alkyd polymer, a long oil to 90 wt.% of modified CNSL resin and about 10 to 50 wt.% alkyd polymer, or mixtures thereof. linseed oil ingredient, based on the weight of the resin-form 14. The stain of claim 1, wherein the stain has a solids ing component. content of at least about -70 wt.% and a VOC content of -300 6. The stain of claim 5, wherein the stain contains 20 to 40 g/l or less. wt.% of a secondary resin, based on the weight of the resin 15. The stain of claim 14, wherein the stain contains about forming component, the secondary resin comprising an oil 50 to 90 wt.% of modified CNSL resin and about 10 to 50 wt. modified urethane, a medium oil alkyd polymer, a long oil % linseed oil ingredient, based on the weight of the resin alkyd polymer, or mixtures thereof. forming component. 7. The stain of claim 1, wherein the linseed oil ingredient is 16. The stain of claim 1, wherein the linseed oil ingredient a heat-bodied linseed oil. is modified linseed oil. 8. The stain of claim 1, wherein the linseed oil ingredient is a copolymer of linseed oil and dicyclopentadiene. c c c c c