NZ624137B2 - Plasticizers for adhesive, coating and sealant compositions applied to asphalt - Google Patents

Abstract

Disclosed is an asphalt adhesive, coating or sealant composition comprising a base polymer or copolymer material and at least one ester containing plasticiser having a molecular weight less than about 3,000 grams per mole and a structure according to formula (I). The composition resists softening of the asphalt at elevated temperatures up to 140°F (60°C). In a particular embodiment, the plasticizer is oxydiethylene dibenzoate, castor oil, and glycerol triacetate. In a particular embodiment, the base polymer or copolymer that includes polyurethanes, silylated polyurethanes,and silylated polyethers. the asphalt at elevated temperatures up to 140°F (60°C). In a particular embodiment, the plasticizer is oxydiethylene dibenzoate, castor oil, and glycerol triacetate. In a particular embodiment, the base polymer or copolymer that includes polyurethanes, silylated polyurethanes,and silylated polyethers.

Description

Attorney Docket No. H0450-410WO TITLE OF THE INVENTION Plasticizers for ve, Coating And Sealant Compositions Applied to Asphalt CROSS REFERENCE TO RELATED APPLICATION

[0002] This application claims the benefit under 35 U.S.C. §119(e) to US. Provisional Patent Application No. 61/5 54,427, filed November 1, 2011, the entire disclosure ofwhich is incorporated herein by reference.

BACKGROUND OF THE INVENTION FIELD OF THE INVENTION

[0003] The invention relates to an adhesive, coating or sealant ition for application to asphalt surfaces, and also for use in construction ts having asphalt substrates or layers.

DESCRIPTION OF RELATED ART Asphalt is used in a variety of applications including road construction and roofing. However, t is very susceptible to degradation Via weather and other chemicals that can attack and disintegrate the t. Accordingly, liquid—applied adhesive products such as sealants and adhesively—attached solid barriers such as air and water barrier membranes can be applied to the asphalt to prevent degradation, provide on, and/or to tie into existing and/or newly installed building products. The adhesive compositions applied to asphalt surfaces typically include a base material such as a r or copolymer and at least one plasticizer which serves to improve the softness and lity of the adhesive composition. The plasticizers embed themselves between the polymer chains thereby decreasing the glass transition temperature, reducing brittleness and stiffiiess, and improving processability.

[0005] Traditional plasticizers used in adhesive, gs and sealant compositions are phthalate-based compounds. US. Patent Reissue No. Re 41,586 s an adhesive material that es a diisodecyl phthalate plasticizer. US. Patent No. 623 describes an adhesive composition that includes dicyclohexyl phthalate and diphenyl phthalate plasticizers. Phthalate—based compounds, however, have been perceived as having a potentially negative effect on human health and the environment. Further, they soften and liquefy many tic compounds.

Disclosed herein is an asphalt-containing substrate having at least one surface and an adhesive, coating or sealant composition applied to the ate surface. It further includes an adhesive, coating or sealant composition that resists softening of an asphaltcontaining substrate to which it is applied up to a softening point of an asphalt compound in the asphalt-containing substrate.

Also disclosed herein is an adhesive, coating or sealant composition that includes at least one base al and at least one cizer. The plasticizer has a AH26(10835307_1):LNB molecular weight less than about 3,000 grams per mole and a structure ing to formula (I), RIJKO/\[~R2] X (I) wherein R is a hydrogen atom; a saturated or unsaturated, functionalized or unfunctionalized, branched or straight chain, alkyl group having 1 to about 50 carbon atoms, a functionalized or unfunctionalized alkanol group having 1 to about 50 carbon atoms or a functionalized or unfunctionalized aryl group having about 6 to about 12 carbon atoms; X is . an Integer from 1 to about 10; and R 1s a hydrogen atom;, a saturated or unsaturated, ed or straight chain, nalized or unfunctionalized alkyl group or ether- containing alkyl group having 1 to about 50 carbon atoms; or an ester-containing group. X is ably from 1 to about 3. R1 is preferably an alkyl group of about 1 to about 50 carbon atoms, but preferably has 1 to about 20 carbon atoms. R1 may also be an alkanol 1 to about 20 carbon atoms. The R2 alkyl group ably has 1 group of preferably about to about 20 carbon atoms. 1 2 In a preferred embodiment, R is a methyl group, and R is an ester—containing 1 to about 10 carbon atoms group that is a reaction product of at least one alcohol having and at least one carboxylic acid having 1 to about 50 carbon atoms. In a more preferred 2 . . . . . embodlment, R. is an ester—containlng group that IS a reaction product of ethylene glycol and acetic acid.

In another preferred embodiment, R is a fatty alcohol having about 8 to about . . . . . 22 carbon atoms, and R IS an ester—contammg group that Is a reactlon product of at least one alcohol having 1 to about 10 carbon atoms and at least one fatty acid having about 8 to ‘ 1 2 about 22 carbon atoms. In a more preferred embodiment, R is 9-heptadecenol and R 15 an ester-containing group that is a reaction product of ethylene glycol and 12-hydroxy—9- octadecenoic acid.

Also disclosed herein are products for use on asphalt-containing substrates that have the adhesive, coating or sealant compositions as described above. The products of the invention may include a liquid applied roofing product such as a water-proofing membrane, a white roof coating, a sealant, a mastic or a caulk. It may also be applied to a building pe comprising roofing, air and water barriers, a damp proofing t, or a roofing produce.

Also disclosed herein is a method for applying the adhesive, coating or sealant itions described above to an asphalt-containing substrate. The method es applying the composition to an asphalt-containing substrate such as a roof to form at least one layer, wherein the composition resists softening of the asphalt-containing substrate up to a softening point of an asphalt compound in the asphalt-containing substrate, and in some preferred embodiments, resists softening up to no greater than about 140oF.

Also disclosed herein is an asphalt-containing substrate having at least one surface and an adhesive, g or sealant composition applied to the at least one substrate surface, wherein the ve ition resists softening of the asphalt-containing substrate up to a softening point of an asphalt compound in the asphalt-containing substrate, and the ve, coating or sealant composition comprises at least one base material and at least one AH26(10835307_1):LNB cizer, wherein the at least one plasticizer has a molecular weight less than about 3,000 grams per mol and a structure according to formula (I), ] According to a first aspect of the present invention there is provided a ition for asphalt substrates comprising a silylated polyether polymer and a plasticizer having a molecular weight less than about 3,000 grams per mole selected from the group consisting of oxydiethylene dibenzoate, glycerol triacetate, polyether polyol and any mixtures thereof; whereby when the composition is applied to the surface of a substrate containing asphalt, the composition causes resistance to softening of the substrate under elevated temperature conditions up to about 60°C. [0019b] According to a second aspect of the present invention there is ed an asphalt containing substrate wherein at least one surface thereof having a layer of the composition of the first aspect of the invention. [0019c] According to a third aspect of the present invention there is provided a method for applying a composition to an t containing substrate sing applying the composition to an asphalt containing substrate to form at least one layer n, wherein the composition comprises about: (a) 5-30 percent by weight of a plasticizer selected from the group consisting of oxydiethylene dibenzoate, glycerol tate, polyether polyol and any mixtures thereof; (b) 10-60 percent by weight of ted polyether polymer; and (c) 5-85 AH26(10835307_1):LNB t by weight of additives comprising calcium carbonate filler and additives comprising adhesion promoters, pigments, UV additives and desiccants; whereby when the composition is applied to the surface of the asphalt containing ate causes resistance to softening of the substrate under elevated temperature conditions up to about 60° C. [0019d] According to a fourth aspect of the present invention there is provided a composition for asphalt substrates consisting essentially of a ted her polymer and a plasticizer having a molecular weight less than about 3,000 grams per mole consisting of ol triacetate; whereby when the composition is applied to the surface of a substrate containing asphalt, the composition causes resistance to softening of the substrate under elevated temperature conditions up to about 60° C.

AH26(10835307_1):LNB above and to an adhesive product for an asphalt surface containing the plasticizer described bed above. a method for applying an adhesive ition ning the cizer With respect to the sealed asphalt substrates or adhesive, coating or sealant compositions used herein, asphalt includes any material primarily composed of natural or processed bitumen. Bitumen compounds are a class of viscous, solid, or semi-solid substances primarily containing high molecular weigh hydrocarbons. The asphalt may cutback t, come in variety of forms including asphalt cement, emulsified asphalt, foamed asphalt, or mastic asphalt. An asphalt substrate is an asphalt-containing substance ' have surfaces or medium to which another substance is applied. The asphalt substrates may that may include, but are not limited to, es of roads, bridges, parking lots, building surfaces such as roofs, waterproofing membranes, white roof coatings, or any other application where asphalt is used. Asphalt es may also include the surfaces of asphalt-based products such as roofing shingles, t membranes and asphaltic layers on laminated building products as well as building envelope systems having roofing, air and ! water barriers, damp proofing products, or other roofing products.

Concerning the adhesive compositions used herein, ve products e that can adhere or bond to surfaces. any products that have an active c0mponent(s) Adhesive compositions used in the adhesive products of the present invention e various types including both solvent—based and hot melt adhesives, or pressure—sensitive, heat—sensitive, moisture—reactive, drying, contact, or light—curing adhesives. The adhesive products, include, but are not d to water-proofing membranes and other similar membranes, sealants, mastics, glues, , and coatings. Coatings may be applied to any surface by any means and may cover all or part of the surface as desired. Sealants may be similarly applied in a manner such that the t composition fills, seals or otherwise covers cracks, es, holes, etc., in the substrate to which the composition is applied.

The ve, coating or sealant compositions herein include at least one plasticizer. The plasticizer is a low molecular weight compound that, when the composition is applied to an asphalt-containing ate, the plasticizer resists softening the substrate at elevated temperatures. The plasticizer preferably has a low molecular weight (i.e., less about 3,000 grams per mole) to prevent a disadvantageous increase in the viscosity of the adhesive ition when mixed. The plasticizer more preferably has a molecular weight ranging from about 150 grams per mole to about 1,500 grams per mole. The plasticizer most preferably has a molecular weight g from about 200 grams per mole to about 950 grams per mole. Further, using the invention, the composition resists softening of an asphalt-containing substrate to which it is applied up to the softening point of an asphalt compound used as or in the asphalt—containing substrate. Such softening points may vary depending on the t compound used. In certain embodiments, the composition s softening of an asphalt-containing substrate to preferably no greater than about 140°F (60°C), but can, in some embodiments, resist softening at higher temperatures. The plasticizer also preferably does not include phthalate due to the perception of potential risks to human health and the environment associated with the phthalate compounds in addition to the tendency of phthalate-based plasticizers to e into the asphaltic substrate and soften the t.

The plasticizer ofthe present invention is preferably represented by the general a (I): leo/\iR2l X (I) wherein in formula (I), x is an integer that ranges from 1 to about 10, preferably from 1 to about 3. R1 may be a en atom or a ted or unsaturated, functionalized or unfunctionalized, branched or straight chain alkyl group of 1 to about 50 carbon atoms, preferably 1 to about 20 carbon atoms. R1 may also be a functionalized or unfunctionalized alkanol group having 1 to about 50 carbon atoms, preferably 1 to about 20 carbon atoms, wherein 18 carbon atoms es castor oil. R1 may r be a functionalized or unfunctionalized aryl group having about 6 to about 12 carbon atoms. Functional groups that may be used on R1 include, but are not limited to aryl groups, aralkyl groups, fluoro, chloro, bromo, iodo, hydroxyl, carbonyl, aldehyde, haloformyl, carbonate ester, carboxylate, carboxyl, ether, ester, hydroperoxy, peroxy, caroxamide, amine, ketimine, aldimine, imide, azide, diimide, cyanate, nate, nitrate, nitrile, nitrosooxy, nitro, nitroso, pydridyl, sulfonyl, sulfo, sulfinyl, sulfino, sulflqydryl, thiocyanate, disulflde, phosphino, phosphono, and phosphate groups. R1 is preferably a fatty alcohol group having about 8 to about 24 carbon atoms, a saturated alkyl group having 1 to about 3 carbon atoms, or an aryl group having 6 to about 8 carbon atoms. R1 is most ably 9-heptadecenol, a methyl group, or benzene.

In formula (I), R2 may be a hydrogen atom or a saturated or unsaturated, branched or straight chain, fimctionalized or unfunctionalized alkyl group having 1 to about 50 carbon atoms, preferably 1 to about 20 carbon atoms. R2 may also be an ester-containing well. Suitable functional groups for group and may further have additional ether linkages as R2 may include those listed above with respect to fimctional groups for R1, but R2 may be independently functionalized with different functional groups than those used on R1. R2 is preferably an ester-containing group which is a reaction product of at least one alcohol having 1 to about 10 carbon atoms, preferably 1 to about 3 carbon atoms, with one or more of the following reactant compounds: at least one carboxylic acid having 1 to about 30 carbon atoms, at least one fatty acid having about 8 to about 24 carbon atoms, or at least one aryl carboxylic acid having 7 to about 30 carbon atoms. R2 is most preferably an ester- containing group which is the reaction product of ethylene and acetic acid, ne glycol and roxy-9—octadecenoic acid, or 2—methoxyethanol and benzoic acid.

[0028] Plasticizers of the present invention can also be formed so as to be an ester- containing reaction product of at least one glycerol and at least one carboxylic acid having about 2 to about 30 carbon atoms or at least one glycol and at least one aryl carboxylic acid having 7 to about 30 carbon atoms. More preferably, the plasticizer is formed as an ester- containing reaction product of glycerol and l2-hydroxyoctadecenoic acid, glycerol and acetic acid, or glycol and benzoic acid.

Thus, the most preferred plasticizers include oxydiethylene dibenzoate, castor oil, glycerol triacetate, and mixtures and ations thereof. These preferred plasticizers have been shown to resist softening an t surface at temperatures up to the standard ing temperature of the asphalt compound material in the asphalt surface, which may vary from compound to compound. In certain embodiments, it resists ing up to about no greater than about 140°F .

The composition also es at least one base material as noted above. The base material may include any compound appropriate for use in an adhesive, coating or sealant composition, preferably at least one polymer. More preferably, the base material will include at least one of polyurethanes, silylated polyurethanes, silylated polyethers, and copolymers thereof. The copolymers may be random, alternating, block, or graft copolymers. Polyurethanes of the invention may be produced through a polymerization on where a monomer containing at least two nate groups reacts with another r with at least two hydroxyl groups in the presence of a catalyst. A non-limiting example of a polyurethane of the ion is ECHELONTM MU 290 produced by the Dow Chemical Company of Midland, Michigan. The silylated polyurethanes may be produced by the polymerization reaction of an amino- or sulfhydryl— functional silane with an isocyanate—terminated polymer or the reaction of an isocyanosilane with a polyol or a hydroxyl-terminated prepolymer. A non-limiting example of a silylated polyurethane of the invention is SPUR+TM produced by Momentive Performance Materials of Columbus, Ohio or Geniosil available from Wacker Silicones of Mfinchen, Germany. The silylated polyethers can be produced by the on of a dimethoxysilane with an allyl-terminated polypropylene glycol. A non-limiting example of a silylated polyether of the invention is MS PolymerTM produced by Kaneka ofPasadena, Texas. These preferred base materials were selected for their resistance to weather, moisture, chemicals, corrosion, and cracking addition to their compatibility with tic compounds and general mechanical properties.

The ve, coating or t compositions herein may also include other additives. These additives may include one or more fillers including, but not limited to aluminium silicate, kaolin clay, aluminum oxide, limestone, barium sulfates, magnesium oxide, calcium carbonate, metal powder or flakes, potassium silicate, calcium silicate, silica, sodium silicates, ceramic beads, strontium sulfate/selestite, clays, talc or magnesium silicate, and dolomite. Other additives e light weight fillers like pumice, glass bubbles, polymeric bubbles and the like, adhesion promoters, desiccants, idants, biocides, fungicides, sts, glass or cellulose fibers, pigments ing, but not limited to carbon black and titanium dioxide, dyes, colorants, brighteners, thickeners, surfactants, tackiflers, UV ers, moisture absorbers, antistatic agents, mold release agents or other physical property modifiers. ably, the ves include calcium carbonate, dessicant, adhesion promoter, catalyst, and at least one pigment.

As discussed above, the adhesive, coating or sealant compositions ofthe present invention include, but are not limited to compositions including at least one base material, plasticizer, and ve. The base material is ably at least one of polyurethanes, silylated polyurethanes and silylated hers, the plasticizer is more preferably oxydiethylene oate, castor oil, glycerol triacetate, and mixtures and combinations thereof, and the preferred additives include calcium carbonate, silica, and carbon black. The weight percent range of the base material in the adhesive is about 10 to about 60 percent by weight ofthe composition, preferably about 10 to about 40 percent. The weight percent to about 20 percent by range of the plasticizer is about 5 to about 30, preferably about . The weight percent range of the additives is about 5 to about 85 percent by weight ofthe composition, preferably about 40 to about 70 t by weight. The weight percent of the composition, range of the calcium carbonate is about 0 to about 70 percent by weight preferably about 40 to about 60 percent.

The products of the present invention may include, but are not limited to liquid products, particularly applied roofing products. The liquid applied roofing products preferably include waterproofing membranes, white roof gs, sealants, mastics, or caulks. The adhesive compositions of the present invention may also be used to adhere membranes, such as water or air barrier membranes or roofing barrier tapes, and similar materials used in building envelope systems, and those Which may be applied to asphalt- containing substrates, preferably by adhering to, coating and/or sealing the substrate surface, for example in a layered ted building products structure having an asphaltic component or layer. The adhesive composition may be d directly to the asphalt surface and/or to at least one surface ofthe membrane.

The present invention also includes a method'for applying an adhesive, coating or sealant composition to an asphalt substrate, preferably Via an upper or outer surface. adhesive, g or t composition can be applied to the asphalt surface using any ’10 suitable que including rolling, spraying, or brushing to form at least one layer of any suitable thickness. The asphalt surface is preferably a building e, and more preferably a roof. After the initial application of ve, g or sealant composition, additional layers of such composition or other building or construction materials such as air or water barrier membranes, tapes, roofing shingles, etc. may be added or d. . [0035] Various cizers were tested to determine whether they would soften asphalt es under elevated temperatures. The non—limiting examples are described below: EXAMPLES [0036} Multiple circular testing areas (“dams”) were constructed on an asphalt surface including 300 pen rubberized t compound. About 20 milliliters of plasticizer were added to each dam. The asphalt surface was then placed in an oven and heated at a temperature of 120°F for about 24 hours, and then up to 155°F. A rub test was then conducted to assess whether the plasticizers softened the asphalt surface. The asphalt area within each dam was then touched with a gloved finger. If the gloved finger showed a dark brown or black residue, the associated plasticizer failed the test.

The testing results are summarized in Table 1.

Table 1 ' Vertellus® Specialties of Indiana - olis, Indiana lus® #1 Castor Oil Vertellus® n® 8 Vertellus® cin® P1 Vertellus® Flexricin® P4 Vertellus® Filtered Neutral Castor Oil lus® Citroflex® A4 Ferro of Cleveland, Ohio Santicizer® 278 Ferro Plaschek® 775 Fail I Ferro Santicizer® 261A I Fail Lanxess of Germany 1 Mesamoll® Fail Lanxess Triacetin® Pass ‘i Emerald Performance KfleX® DE Pass Materials of Cuyahoga Falls, Ohio Bayer Material Science of Arcol® PPG-3025 Pass Germany Mesamoll®, Santicizer® 278, and Santicizer® 261A are ional, phthalate- based plasticizers and were tested for ison purposes. Further, the Arcol® PPG—3025 is a high molecular weight plasticizer with 2 hydroxyl groups per chain. Thus, although the Arcol® PPG-3025 plasticizer passed the rub test, it was considered unsuitable for the of the present invention due to the goal of maintaining good viscosity and controlling tack adhesive composition.

Each plasticizer that passed the rub test was added to a basic sealant formula prepared having the following components: polyether polyol plasticizer (10-30 parts), calcium carbonate filler (3 0-60 parts), silylated polyether polymer (15-30 parts), additives including pigments, adhesion promoters, UV additives, and desiccants (15-50 parts) and retested to determine whether a tcontaining the exemplary plasticizer would resist softening of asphalt es. For this test, multiple asphaltic compounds were used including Henry G100 S/S (asphalt base or protection sheet, rubber modified fiberglass reinforced). The sealant containing the cizer was d to each asphalt surface using the same method described above and the asphalt surface was placed in an oven at a temperature of 120°F, and subsequently up to 155° for 7 days. A rub test was then conducted to assess whether the sealants ning the plasticizers softened the asphalt surface. All of the sealants containing a plasticizer ing to the invention passed the rub tests.

It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive t thereof. It is understood, ore, that this invention is not limited to the particular embodiments disclosed, but it is intended to cover modifications within the spirit and scope ofthe present invention as defined by the appended claims.

Claims (12)

We claim:

1. A composition for asphalt substrates comprising a silylated polyether polymer and a plasticizer having a molecular weight less than about 3,000 grams per mole selected from the group consisting of oxydiethylene dibenzoate, glycerol triacetate, polyether polyol and any mixtures thereof; whereby when the composition is applied to the surface of a substrate containing asphalt, the composition causes resistance to softening of the substrate under elevated temperature conditions up to about 60°C.

2. The composition of claim 1 wherein the composition is a sealant for an asphalt ate.

3. The composition of claim 1 wherein the composition is an adhesive for an asphalt ate.

4. The composition of claim 1 wherein the composition is a coating for an asphalt ate.

5. The composition of any one of claims 1 to 4 wherein the plasticizer consists of oxydiethylene dibenzoate.

6. The composition of any one of claims 1 to 4 wherein the plasticizer ts of glycerol triacetate.

7. The composition of any one of claims 1 to 4 wherein the plasticizer consists of polyether polyol.

8. The composition of any one of claims 1 to 4 comprising about a. 5-30 percent by weight of a plasticizer selected from the group consisting of oxydiethylene dibenzoate, glycerol triacetate, polyether polyol and any es thereof; b. 10-60 percent by weight of ted polyether polymer; and c. 5-85 t by weight of additives comprising calcium carbonate filler and ves sing adhesion promoters, pigments, UV additives and desiccants.

9. An asphalt containing ate wherein at least one surface thereof having a layer of the composition of claim 8. 10833665

10. A method for applying a composition to an asphalt containing substrate comprising applying the composition to an asphalt containing substrate to form at least one layer thereon, wherein the composition ses about: a. 5-30 percent by weight of a plasticizer selected from the group consisting of oxydiethylene dibenzoate, glycerol triacetate, polyether polyol and any mixtures thereof; b. 10-60 percent by weight of silylated polyether polymer; and c. 5-85 percent by weight of additives comprising calcium carbonate filler and additives comprising adhesion promoters, pigments, UV additives and desiccants; whereby when the composition is applied to the surface of the asphalt containing substrate causes resistance to softening of the substrate under elevated temperature conditions up to about 60° C.

11. A composition for asphalt substrates consisting essentially of a silylated polyether polymer and a plasticizer having a lar weight less than about 3,000 grams per mole consisting of glycerol triacetate; whereby when the composition is d to the surface of a substrate containing t, the composition causes resistance to softening of the substrate under elevated temperature conditions up to about 60° C.

12. The composition of claim 11 consisting essentially of about a. 5-30 percent by weight of a plasticizer consisting of glycerol tate; b. 10-60 t by weight of silylated polyether polymer; and c. 5-85 percent by weight of additives sing m carbonate filler and additives sing adhesion promoters, pigments, UV ves and desiccants. Henry Company LLC By the Attorneys for the Applicant N & FERGUSON Per: 10833665