CA2193720A1 - Striping composition and method for striping a road or highway surface - Google Patents
Striping composition and method for striping a road or highway surfaceInfo
- Publication number
- CA2193720A1 CA2193720A1 CA002193720A CA2193720A CA2193720A1 CA 2193720 A1 CA2193720 A1 CA 2193720A1 CA 002193720 A CA002193720 A CA 002193720A CA 2193720 A CA2193720 A CA 2193720A CA 2193720 A1 CA2193720 A1 CA 2193720A1
- Authority
- CA
- Canada
- Prior art keywords
- striping
- composition
- road
- cure
- striping composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/725—Combination of polyisocyanates of C08G18/78 with other polyisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/004—Reflecting paints; Signal paints
-
- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01F—ADDITIONAL WORK, SUCH AS EQUIPPING ROADS OR THE CONSTRUCTION OF PLATFORMS, HELICOPTER LANDING STAGES, SIGNS, SNOW FENCES, OR THE LIKE
- E01F9/00—Arrangement of road signs or traffic signals; Arrangements for enforcing caution
- E01F9/50—Road surface markings; Kerbs or road edgings, specially adapted for alerting road users
- E01F9/576—Traffic lines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
- C08G2150/50—Compositions for coatings applied by spraying at least two streams of reaction components
Abstract
The disclosed striping composition provides a fast cure on road or highway surfaces . The striping composition is a two-part (part A and part B) polyurethane forming system having good adhesion characteristics to a road or highway surface, and weathering and yellowing resistance over time. Part A contains an aliphatic polyol and part B
contains an aliphatic polyisocyanate.
contains an aliphatic polyisocyanate.
Description
2193~2~
-- STRIPING ~O~POSITION ~ MET~OI~ FO~
STRIPING A ROAD OR H~¢HWAY SURFACE
S Flela af ~che l~elltion This inventic~n relates to a striping composit.ion for use on a road or highway su:rface, a method for striping or marking a road or hi~hway surface, and the resu 1 tin~
striped or marked road or highway. The s~riping composition is a two-part polyurethane formin~ system having fast cure properties; good adhesion characteristics to a r~a.d or highway surface; good weathering and abrasi.on resi~tan.ce; ~nd ambering resistance over time.
~ac~round of the Invent~ OD.
Various stripin~ or marking compo~itions have ~een used on roads and highway~ ~or many years. The first class of striping compositions used on roadc and hi.ghways with some succ~ss were alkyd-based paint com~o~itions such as those disclosed in U,S. Patent Nos. 2,8~7,732; 2,897,733;
and 3,326,098. Alkyd-based paint ~ompositi.on~ a~e generally slow to dry and contain ester linkages which ~re ~u~c~ptible ~o h~drolysis fre~. the alkaline condition of roads. This hydrolysis, in part, causes the appli.ed paint 2S tv have poor wear resistance. Accordi~.gly, i~ is desirea~le t~ provide a striping compositi.on h~ving a much faster cure time and im~roved wear resistance.
Most alkyd-based paint compositions require the addition ~f a sol~ent o~ d~ying oil to decrease the viscosity so that the pai~ composition can be spra~e~ onto road surfaces. For example, see U.S. Patent No. 3,326,098.
~he presence o~ a solvent during highway marking create5 a pollution problem since ~he solvent eva~?orates into the atmosphere. Accordingly, i t is desireable to provide 21~3720 striping ~ompositi.on which is 100% solids, and does not contain solvents or dryi ng oils .
As an alt:ernative to alkyd-b~sed paint composi~ions, solvent free epoxy-ba6ed stri.pi.ng S compositions were developed. Epoxy-ba.~ed stxiping compositions are described in detail in U . S . Patent Nos.
4, 088, 633; 4, 185, 132; and 4, 25~, 468 . These stripi ng compvsitions a~e a si~nificant improvement over prior alkyd-based paints in terms of alkaline and wear re~istance, and in reducing the need for solvents during application. In particular, the ~.poxy-based striping com~ositions are better at withstandin~ water immersion comp~red with the alkyds. In addition, they provide a better bond to glass beads dropped thereon which is important for providing retroreflectivity at night.
Increased adhesion to glas~ beads provides bett~r retention of the glass beads to the road ~urface for a lon~er period of time. Epoxy-based striping composition~, however, are still generally too slow in ~uring, particularly on a cold road surface. In addition, they age harden and become brittle, and have a tendency to amber. A~ a result of the slo~.Curi.ng rate ~or su~h epoxv-~a~ed str.ipin~
compositi~ns, it is necessary to put cones alon.~ the striping composition applied to a road surface to prevent.
cars tra~eling along the road from tracking the uncured compvsition~ The necessity for coning while the epoxy-based striping composition cures increases the cost o~
striping a road by requiring a num~er of cones sufficient to prevent cars and trucks from tracking the stri.ping composition befo~e it cures, and by provi.ding the necess.ity for employing crews to put the cones down once the st.riping composi~ion is applied and to pick the cones up once it 2193721~
. .
- _ cure~. Accordingly, it would ~e desirable to stripe a road.
with a composition tha~ is fast cure, e~en on cold road surfaces, in order to eliminate the need ~or conin~ and thereby enhance striping effi~iency.
Furthermore, it would be desireable to provide a fast cure stripin~ comp~sition having good ~dhesion characteristics to road or highway surfaees and which can withstand ~eathering and which will not significantly amber over time.
SummarY o~ the I~ve~tion A striping composition for use on a road. or highway surface, a method for striping a road or hi~hway s~rface, and a striped road or highway surface ~e provided by the present invention. ~he stripi~g composition has fast cure properties, has good adhesion characteri.sti~s to a road or high.way surface; ~ood weathering and abra~ion resistan~e; ~nd ambering resistance over time.
The striping composition for u~e on a road or highway surface according to the pre~ent .invention is prepared ~rom a two-part polyu~ethane fo~ming .system containin~ a first part !Pa t A) ~n~.~ second p~rt ~part B). Part A co~tains an isocyanate-reactive group-containing component and part s contains an ~s~cyanate group-containing component. Parts A and B react to form a.
polyure~hane system.
Part A ~ the polyurethane formi~g system can contain any polyol capable o~ reacting with the polyisocyanate in part ~. The polyol component is seleeted based upon the desLred properties o~ the fi.nal polyurethane composition, which include adhe~ivene~s, amber resistance, strength and flexibility, and upon the desired prope~ties 219372~
of part A, which include viscosity and reacti.vity In order to provide these properties, the polyol component can be a mixture of polyols Polyols usefu]. in part A
prefer~hly include c~m~un~s and polymers which are diols, triols, and tet~aols. The hydxoxyl groups can be primary, secondary or tertiary.
The polyol compounds and polymers can be glycols, alkane polyols which are lower (~1 - C10) or higher (Cll -C,a), polyethe~ poly~ls, epoxy resins, and monosaecharides.
Preferably, part A contain6 a mixture of polyols such as, for example, a mixture of a secan~ary die~her diol and a lower polyalkylene glycol. Preferably, the secondary diether ~iol is ~he diether of propylene glycol and bisphenol A, and the lo~er polyalkylene glycol .is tripropylene glycol, Part B of the polyurethane ~ystem can be any polyisocyanate capable of reacting with the polyol in part A to provide a fast cure striping composition having a de~irable degxee of adhesion to a road or highway sllrface, ~0 strength and flexibility, and amber resistance over t.ime, and which will pro~ide a part B having a desired degree of reactivity and a viscosity suf LiCieIlt f~r p.-ocess~g i-,l commercial s~rip~ng or marking machinery without the use o~
solvents. Mixture~ of polyisocyanates can be used.
ALiphatic and cycloaliphatic polyisocyanate are desira~le becau~e they tend t~ produce polyurethane~ ha~ing decreased amber~ng. 'rrimeri~ed hexamethylene diisocyanate ~H~I), a trifunction~l isocyanurate, is a preferred alipha~ic polyisocyanate. In ~rder to increa.se the reactivity and decrease the visc05ity of part B, and provide a harder polyu~ethane, any colorless or lightly colored aromatic polyisocyanates can be used in combination wit~ the 7~ ~
~ alipha~ic ar cycloaliphatic polyisocyanate. Di.phenyl methane diisocyanate ~e.~., diphenyl methane-2,4'- and/or -4,4'-diisocyanate) is a preferred aromatic polyi.socyanate b~cause it is very lightly colored. This aroma~ic polyisocyanate component is particularly advantageous when it is combined with trimerized hexamethylene di.i~ocyanate Generally, if the s~riping composition is unc~lred, either parts A and B have not been combined or parts A and B have been combined bu~ the co~bination has not resulte~
in a cured polyurethane system. Whi.le the striping composltion is uncured, reflectorizing f.iller can he added thereto to provide a cured stripin~ compo~ition having desired retroreflectivity.
The present invention provides a method for 15 s~riping a road or highway surface which int~olves com~ining part A containing isocyana~e~reactive group-contai.ning components and part B containing isocyanate group-containing components to form a reacting striping compo~ition, applying the reactin~ striping composi tion to a ~oad or highway surface, and allowin~ the reacting striping composition to cure and adhere to the road or highw~y surface. If de~ired, reflectori~in~ ~iller C2~ be added to the reactin~ striping composition to provide a striped road or highway su~face ha~lng retroreflectivity 25 effect.
Parts A and B ~:an be applied to a r~ad or highway surface using an app].ica~or which can he a commercially available striping or marking ~pparatus ~o form a film on the road or highway surface. Generally, the film will hat~e a thickness of about 4 mm ~o about 20 mm depending on whether reflectorizing filler is incorpo~ated therein.
219~3729 Detailed De8cri~tio~ of ~he I~vent~on The striping cOmpOSitiOIl ef the ;nven~ion can be 100% solids. The term 'solids" in thi.s context is borrowed from paint chemistry, wherein "solids" includes any components (be they liquid or solid) which becomes a part of the ultimately obtained solid coating. Th.at is, the term ~solids~ excludes essentially volatile solvents or carriers. The phra~e l'essential.ly volatile" is meant to include a li~uid ~hich ha~ a. boiling point or initial boiling point below 150~C at normal atmospheric pressure.
The st~iping composition can have fast cure propertie~. The phrase "fast cu~e~ has been used i.n ~he prior art to describe a striping composi.tion having a "no track time" of about 5 - 10 minutes at room temperature.
See U.S. Patent No. 4,255,468. As used h~rein, the phrase ~'fast cure~ is inte~ded to describe a strip.ing compo~ition which achieves a ~no track time" in at le~t about four minutes at room ~emperature. The ~no tracking time" i~
de~ined as the amount of time necessary for the striping ~0 composition, ence applied to a road or hi~hway surface, to cure to an extent sufficient to re.sist tracking by standard automobile and ~ruck tr~ffic. Preferakly, ~he no ~a~k ~ime is an amount of time sufficient to elimina.te the need for coning to pre~ent tracking without ~ignificantly di~rupting regular traffic pat~erns. More preferably, the no track time is less than 2 minutes, e~en more preferably 10 ~econds to about 50 seconds, and most preferably, ahout 20 seconds to about 4t~ seconds at 75~F.
It is desireable for the striping ~omposition to be relatively '~no track.'~ "Instant no track" may be possible from an application and curing standpoint but it i8 usually desirable to have an " open time" to both wet the _ surface of the road or highway and to recei~e the glass beads. If the curing polymerization is too rapid, the resultiny striping composition has too much cohesion. and not enough adhesion ~o the road or highway surface.
Although it is desireable to decrease no track t~me, it should not be so short as to seriousl.y sacrifice a &esion to a road or highway ~u~face. For most applications, a no track time of 20 or 30 seconds is sufficient to provide adequate adhe~ion at room temperature (75~F). On. cold surfaces, it may be desi~able to provide a longer no track time in order ~o provide sufficient adhesion to the r~ad or hi~hway surface. Wh.ile providing fast cure propexties, the striping compo~ition ~f the pre~ent in~ention adheres sufficiently well to a road or highway surface ~o that it lS has a long life expectancy and can resist peelin~ or abrasion caused by traffi.c including sno~ plows.
The striping composition can be applied to any type of road sur~ace. ~refer~bly, the road ~urface is made o~ asphalt or concrete upon which the striping composition of the present inventi.on adhe~es very well since it is porous. Although the striping composition adheres we]l to most ro~d or highw~y surfaces, i' can adhere sli~htl~ t~
other less porous surfaces such as metal. This property helps prevent the striping composition from adhering to the applicator. If de~ired, the ~triping compositi~n can be applied to a porous road ~urface with as much force as desired to ensu~e cufficient adhesion thereto.
Part ~ !3y~t~n This invention contemplates the use of an isocyanate-reactive group-containi.n~ component (pa.rt A) capable of reacting with the isocyanate gro~p-containing component contained in part B to provide a fast cure striping compo~ition. The isocyanate-reacti.ve gxoup-c~ntaining component preferably contains polyols or thiols The polyol component is selected ba~ed upon t~e desired proper~ies of the final polyurethane com~osition, wh.ich include adhesiveness, amber resi.st~nce strength and flex~bility, and upon the desired properties of part A, which include viscosity and reactivity. In order to provide these properties, the polyol component can h~ a mixture of polyols. Exemplary polyols which can be u~ed to form non-yellowing or non-amberi.ng pol~lrethanes are generally described in U.S. Patent Nos. 4,604,A18 And 5,159,045, which are incorporated herein by reference.
These polyols include compounds and polyme~s which are diols, ~riols, and ~etraols.
The compounds and polymers include, ~o~ example, glycols such as ethylene glycol, propylene gLycol, ~
dihydro~ye~hyl ether (diethylene glycol), dipropylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,6-hexameth.ylene glycol, neopentyl glycol, polyethylene g~ycol, polyp~opylene glycol, polypropylene-polyethylene glycol and polybutylene glycol; al~ane polyols such as glycerol, trimethylolpropane, hexanetriol., pentaeryt~,ritol., xylitol and sorbitol; polyethe~ polyols obtained ~y addition polymerization of a single compound o~ a mixture
-- STRIPING ~O~POSITION ~ MET~OI~ FO~
STRIPING A ROAD OR H~¢HWAY SURFACE
S Flela af ~che l~elltion This inventic~n relates to a striping composit.ion for use on a road or highway su:rface, a method for striping or marking a road or hi~hway surface, and the resu 1 tin~
striped or marked road or highway. The s~riping composition is a two-part polyurethane formin~ system having fast cure properties; good adhesion characteristics to a r~a.d or highway surface; good weathering and abrasi.on resi~tan.ce; ~nd ambering resistance over time.
~ac~round of the Invent~ OD.
Various stripin~ or marking compo~itions have ~een used on roads and highway~ ~or many years. The first class of striping compositions used on roadc and hi.ghways with some succ~ss were alkyd-based paint com~o~itions such as those disclosed in U,S. Patent Nos. 2,8~7,732; 2,897,733;
and 3,326,098. Alkyd-based paint ~ompositi.on~ a~e generally slow to dry and contain ester linkages which ~re ~u~c~ptible ~o h~drolysis fre~. the alkaline condition of roads. This hydrolysis, in part, causes the appli.ed paint 2S tv have poor wear resistance. Accordi~.gly, i~ is desirea~le t~ provide a striping compositi.on h~ving a much faster cure time and im~roved wear resistance.
Most alkyd-based paint compositions require the addition ~f a sol~ent o~ d~ying oil to decrease the viscosity so that the pai~ composition can be spra~e~ onto road surfaces. For example, see U.S. Patent No. 3,326,098.
~he presence o~ a solvent during highway marking create5 a pollution problem since ~he solvent eva~?orates into the atmosphere. Accordingly, i t is desireable to provide 21~3720 striping ~ompositi.on which is 100% solids, and does not contain solvents or dryi ng oils .
As an alt:ernative to alkyd-b~sed paint composi~ions, solvent free epoxy-ba6ed stri.pi.ng S compositions were developed. Epoxy-ba.~ed stxiping compositions are described in detail in U . S . Patent Nos.
4, 088, 633; 4, 185, 132; and 4, 25~, 468 . These stripi ng compvsitions a~e a si~nificant improvement over prior alkyd-based paints in terms of alkaline and wear re~istance, and in reducing the need for solvents during application. In particular, the ~.poxy-based striping com~ositions are better at withstandin~ water immersion comp~red with the alkyds. In addition, they provide a better bond to glass beads dropped thereon which is important for providing retroreflectivity at night.
Increased adhesion to glas~ beads provides bett~r retention of the glass beads to the road ~urface for a lon~er period of time. Epoxy-based striping composition~, however, are still generally too slow in ~uring, particularly on a cold road surface. In addition, they age harden and become brittle, and have a tendency to amber. A~ a result of the slo~.Curi.ng rate ~or su~h epoxv-~a~ed str.ipin~
compositi~ns, it is necessary to put cones alon.~ the striping composition applied to a road surface to prevent.
cars tra~eling along the road from tracking the uncured compvsition~ The necessity for coning while the epoxy-based striping composition cures increases the cost o~
striping a road by requiring a num~er of cones sufficient to prevent cars and trucks from tracking the stri.ping composition befo~e it cures, and by provi.ding the necess.ity for employing crews to put the cones down once the st.riping composi~ion is applied and to pick the cones up once it 2193721~
. .
- _ cure~. Accordingly, it would ~e desirable to stripe a road.
with a composition tha~ is fast cure, e~en on cold road surfaces, in order to eliminate the need ~or conin~ and thereby enhance striping effi~iency.
Furthermore, it would be desireable to provide a fast cure stripin~ comp~sition having good ~dhesion characteristics to road or highway surfaees and which can withstand ~eathering and which will not significantly amber over time.
SummarY o~ the I~ve~tion A striping composition for use on a road. or highway surface, a method for striping a road or hi~hway s~rface, and a striped road or highway surface ~e provided by the present invention. ~he stripi~g composition has fast cure properties, has good adhesion characteri.sti~s to a road or high.way surface; ~ood weathering and abra~ion resistan~e; ~nd ambering resistance over time.
The striping composition for u~e on a road or highway surface according to the pre~ent .invention is prepared ~rom a two-part polyu~ethane fo~ming .system containin~ a first part !Pa t A) ~n~.~ second p~rt ~part B). Part A co~tains an isocyanate-reactive group-containing component and part s contains an ~s~cyanate group-containing component. Parts A and B react to form a.
polyure~hane system.
Part A ~ the polyurethane formi~g system can contain any polyol capable o~ reacting with the polyisocyanate in part ~. The polyol component is seleeted based upon the desLred properties o~ the fi.nal polyurethane composition, which include adhe~ivene~s, amber resistance, strength and flexibility, and upon the desired prope~ties 219372~
of part A, which include viscosity and reacti.vity In order to provide these properties, the polyol component can be a mixture of polyols Polyols usefu]. in part A
prefer~hly include c~m~un~s and polymers which are diols, triols, and tet~aols. The hydxoxyl groups can be primary, secondary or tertiary.
The polyol compounds and polymers can be glycols, alkane polyols which are lower (~1 - C10) or higher (Cll -C,a), polyethe~ poly~ls, epoxy resins, and monosaecharides.
Preferably, part A contain6 a mixture of polyols such as, for example, a mixture of a secan~ary die~her diol and a lower polyalkylene glycol. Preferably, the secondary diether ~iol is ~he diether of propylene glycol and bisphenol A, and the lo~er polyalkylene glycol .is tripropylene glycol, Part B of the polyurethane ~ystem can be any polyisocyanate capable of reacting with the polyol in part A to provide a fast cure striping composition having a de~irable degxee of adhesion to a road or highway sllrface, ~0 strength and flexibility, and amber resistance over t.ime, and which will pro~ide a part B having a desired degree of reactivity and a viscosity suf LiCieIlt f~r p.-ocess~g i-,l commercial s~rip~ng or marking machinery without the use o~
solvents. Mixture~ of polyisocyanates can be used.
ALiphatic and cycloaliphatic polyisocyanate are desira~le becau~e they tend t~ produce polyurethane~ ha~ing decreased amber~ng. 'rrimeri~ed hexamethylene diisocyanate ~H~I), a trifunction~l isocyanurate, is a preferred alipha~ic polyisocyanate. In ~rder to increa.se the reactivity and decrease the visc05ity of part B, and provide a harder polyu~ethane, any colorless or lightly colored aromatic polyisocyanates can be used in combination wit~ the 7~ ~
~ alipha~ic ar cycloaliphatic polyisocyanate. Di.phenyl methane diisocyanate ~e.~., diphenyl methane-2,4'- and/or -4,4'-diisocyanate) is a preferred aromatic polyi.socyanate b~cause it is very lightly colored. This aroma~ic polyisocyanate component is particularly advantageous when it is combined with trimerized hexamethylene di.i~ocyanate Generally, if the s~riping composition is unc~lred, either parts A and B have not been combined or parts A and B have been combined bu~ the co~bination has not resulte~
in a cured polyurethane system. Whi.le the striping composltion is uncured, reflectorizing f.iller can he added thereto to provide a cured stripin~ compo~ition having desired retroreflectivity.
The present invention provides a method for 15 s~riping a road or highway surface which int~olves com~ining part A containing isocyana~e~reactive group-contai.ning components and part B containing isocyanate group-containing components to form a reacting striping compo~ition, applying the reactin~ striping composi tion to a ~oad or highway surface, and allowin~ the reacting striping composition to cure and adhere to the road or highw~y surface. If de~ired, reflectori~in~ ~iller C2~ be added to the reactin~ striping composition to provide a striped road or highway su~face ha~lng retroreflectivity 25 effect.
Parts A and B ~:an be applied to a r~ad or highway surface using an app].ica~or which can he a commercially available striping or marking ~pparatus ~o form a film on the road or highway surface. Generally, the film will hat~e a thickness of about 4 mm ~o about 20 mm depending on whether reflectorizing filler is incorpo~ated therein.
219~3729 Detailed De8cri~tio~ of ~he I~vent~on The striping cOmpOSitiOIl ef the ;nven~ion can be 100% solids. The term 'solids" in thi.s context is borrowed from paint chemistry, wherein "solids" includes any components (be they liquid or solid) which becomes a part of the ultimately obtained solid coating. Th.at is, the term ~solids~ excludes essentially volatile solvents or carriers. The phra~e l'essential.ly volatile" is meant to include a li~uid ~hich ha~ a. boiling point or initial boiling point below 150~C at normal atmospheric pressure.
The st~iping composition can have fast cure propertie~. The phrase "fast cu~e~ has been used i.n ~he prior art to describe a striping composi.tion having a "no track time" of about 5 - 10 minutes at room temperature.
See U.S. Patent No. 4,255,468. As used h~rein, the phrase ~'fast cure~ is inte~ded to describe a strip.ing compo~ition which achieves a ~no track time" in at le~t about four minutes at room ~emperature. The ~no tracking time" i~
de~ined as the amount of time necessary for the striping ~0 composition, ence applied to a road or hi~hway surface, to cure to an extent sufficient to re.sist tracking by standard automobile and ~ruck tr~ffic. Preferakly, ~he no ~a~k ~ime is an amount of time sufficient to elimina.te the need for coning to pre~ent tracking without ~ignificantly di~rupting regular traffic pat~erns. More preferably, the no track time is less than 2 minutes, e~en more preferably 10 ~econds to about 50 seconds, and most preferably, ahout 20 seconds to about 4t~ seconds at 75~F.
It is desireable for the striping ~omposition to be relatively '~no track.'~ "Instant no track" may be possible from an application and curing standpoint but it i8 usually desirable to have an " open time" to both wet the _ surface of the road or highway and to recei~e the glass beads. If the curing polymerization is too rapid, the resultiny striping composition has too much cohesion. and not enough adhesion ~o the road or highway surface.
Although it is desireable to decrease no track t~me, it should not be so short as to seriousl.y sacrifice a &esion to a road or highway ~u~face. For most applications, a no track time of 20 or 30 seconds is sufficient to provide adequate adhe~ion at room temperature (75~F). On. cold surfaces, it may be desi~able to provide a longer no track time in order ~o provide sufficient adhesion to the r~ad or hi~hway surface. Wh.ile providing fast cure propexties, the striping compo~ition ~f the pre~ent in~ention adheres sufficiently well to a road or highway surface ~o that it lS has a long life expectancy and can resist peelin~ or abrasion caused by traffi.c including sno~ plows.
The striping composition can be applied to any type of road sur~ace. ~refer~bly, the road ~urface is made o~ asphalt or concrete upon which the striping composition of the present inventi.on adhe~es very well since it is porous. Although the striping composition adheres we]l to most ro~d or highw~y surfaces, i' can adhere sli~htl~ t~
other less porous surfaces such as metal. This property helps prevent the striping composition from adhering to the applicator. If de~ired, the ~triping compositi~n can be applied to a porous road ~urface with as much force as desired to ensu~e cufficient adhesion thereto.
Part ~ !3y~t~n This invention contemplates the use of an isocyanate-reactive group-containi.n~ component (pa.rt A) capable of reacting with the isocyanate gro~p-containing component contained in part B to provide a fast cure striping compo~ition. The isocyanate-reacti.ve gxoup-c~ntaining component preferably contains polyols or thiols The polyol component is selected ba~ed upon t~e desired proper~ies of the final polyurethane com~osition, wh.ich include adhesiveness, amber resi.st~nce strength and flex~bility, and upon the desired properties of part A, which include viscosity and reactivity. In order to provide these properties, the polyol component can h~ a mixture of polyols. Exemplary polyols which can be u~ed to form non-yellowing or non-amberi.ng pol~lrethanes are generally described in U.S. Patent Nos. 4,604,A18 And 5,159,045, which are incorporated herein by reference.
These polyols include compounds and polyme~s which are diols, ~riols, and ~etraols.
The compounds and polymers include, ~o~ example, glycols such as ethylene glycol, propylene gLycol, ~
dihydro~ye~hyl ether (diethylene glycol), dipropylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,6-hexameth.ylene glycol, neopentyl glycol, polyethylene g~ycol, polyp~opylene glycol, polypropylene-polyethylene glycol and polybutylene glycol; al~ane polyols such as glycerol, trimethylolpropane, hexanetriol., pentaeryt~,ritol., xylitol and sorbitol; polyethe~ polyols obtained ~y addition polymerization of a single compound o~ a mixture
2~ of alkylene oxide such as ethylene oxide, propylene oxide and 1,2-butylene oxide to a single compound or a mixture o~
polyhydric alcohols such as glycerol and propylene glycol or polyfunctional compounds such a~ ethylene diamine a~d ethanolamine; epoxy resins of no~olak type, ~-methylepichloro type, cyclooxirane t~pe, gl.ycidyl ethertype, glycidyl ester type, gl.ycoL ether ~xpe, epoxylated unsaturated fatty acid type, epoxylated fatty acid ester -type, polybasic ca.rhoxylic acid ester type, amino-glycidyl type, halogenated type and resorcino] type; and monosaccharides or derivatives thereo~ .selected from fructose, glucose, ~ccharo.se, lac~ose or 2-S methylglucoxide.
For most applications, howe~er, p~lyols containingester groups are not preferred becau~e they tend to hydrolyze in the presence of alkaline present on road surface~. Un~aturation also tends to hydro3ize in the presence of alkaline. If de.sired, polyester~ and polyacrylates or other unsa~urated polymers can be used.
Such polymers are well known in the art.
Part A prefe~abl~ contains a mixture of a secondary diether dîol ~nd a lower polyalkylene glycol 15 component. A lower po~yalkylene glycol is meant to include polymers of glycols wherein the glycols have 2 - 10 carbon atoms. The second.ary diether diol provide~ the backbone for the stripin~ composition and i~ preferably a diether of propylene glycol and bisphen~l A ~hich is comme~cially av~ilabl.e under the tradem~rk DOW RESIN 5~5, a product of Dow Chemical ('o The lower po].ya.lkylene glycol i.s pr~'erably tripropylene glycol. 'Tlhe ~econda~y diether diol is preferably pre~ent in an amount ranging from about 30-90% by weight ~ased on the total. reactant weight in part A, and more preferably about 50-80~ by weight. At ~reater amounts o~ this component, the st~ipi~g composition becomes too soft. ~he ].ower alk~le~ glycol can be present in an amount ranging from 10-'70~ by weight based on the to~al reac~ant weight in part A, and more preferably about 20-40 by ~eigh~. At greater amounts o~ this component, the striping compo~ition becomes too brittle -- T~e Part B S~ t~L
This inventi~n contempla~es ~he use of an i~ocy~nate group-co~taining component ~part B) ca.pable of reacting with the isocyanate-reactive group-contAinin.
component~ contained in part A to provide a fast cure st~iping composition. The isocyanate group-containin~
component (part ~) preferably contains polyisocyana~es having a sufficient visc06ity which will allow part s to ~e processed through road striping apparatus without the use of solvents. The poly~socyanates should he capable of re~ctin~ with ~he polyols in part A to form a pol~lrethane system which will not significantly amber over time.
Aliphatic ~nd cycloalipha~ic polyiso~yanate are preferably used in part B because they tend to produce polyurethanes having decreased ambering. Generall~, aliphatic and cyclo~liphatic polyisocyanates whi.ch can be used in the pre~ent invention correspo~d to the formula Q ( NCO ) n in which n is an integer 2 to 4, and Q repre~ents an aliphatic hydrocarbon radical contain~n~ ~om 2 to 100 carbon atoms, and 7.ero to 50 heteroatoms, or a ~ycloaliphatic hydrccarbon radical coQtaining ~rom 4 to 100 carbon atoms and zero to 5() heter~atom~. Examples of alip~a~ic and cycloaliphatic polyisocyanates incl~de e~hylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, trimethy].h~xamethylene dii90cyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-l,3- and -1,4-dii.socyanate ~nd mixture of thos~ isomers, and l-isocyana~e-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane. Prefe.rred aliphatic and cycloaliphatic polyisocyanates are hexamethylene diisocyana~e, its isocyanurate an~ .its biuret a.nd ~.-~.0 219~ 0 isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane (isophorone diisocyanate). More preferably, the polyisocyanate is trimeri~ed hexamethylene diisocyanate ~DI~, a trifunctional isocyanurate. A commercially av~ilable trimerized hexamethylene diisocyanate is sold under the trademark DESMODUR N-3300 by Miles, Ine.
l'he use of aliphatic or cycloali.phati~
polyisocyanates a~ the only isocyanate group-containi.n~
components in par~ B can produce a sy~tem having a viscosity which is too high ~or convenient use in con~ercial road striping equipment. Ac~ording to the present inventio~, it is possible to replace part of the aliphatic or cycloaliphatic polyisocyanate with an aromatic polyisocyanate. Aromatic polyisocyanates can be useful because they tend to ~ve a viscosi~y decreasing effect when mixed with aliphatic or cycloaliphatic poLy~ocyanates and because they tend to react quickly. In addition, aromatic polyisocyanates tend to provide a faster reaction time and a harder finish. Aliphatic iso~yanates tend to a ~0 p~oduce softer polyure~hane but are more light stable.
Unfortunatel~, most aromatic polyisocyanates are brown and tend to produce yellow or bro~.~ polyurethanes. H~we~-er, by using an ar<~matic polyiso~yana~e which is colorless or on.ly very slightly colored, it is possible to produce a 2S polyurethane which retainS good amber r~ tant p~op~rties.
One skilled in the art wi~ 1 readily appreciate that the aro~atic polyisocyanate should be present in an ~mount suffici~nt to decrease the viscosity of part a $O it can be processed through road stripin~ e~ipment but within a 3V range ~ufficient to pre~ent signi~icant y~llowin~ or amberin~ of the xesulting polyurethane.
219~720 Diphenyl mel-hane d~isocyana~e ~e.g., diphenyl methane-2,4~- and/or -4,4'-diisocyanate~ is a prefer~ed aromatic polyisocyanate because it is ve~y lightly colored.
This aroma~ic polyisocyanate component i5 p~rticularly advantageous because when it is combined with trimerized hexamethylene diisocy~nate, a polyurethane resin can be produced which does not si~ni~icantly amber. Diphenyl methane diiso~yanate is commercially a~ail~ble lm der the trademark LUP~ANATE MP-~02 sold ~y RASF Corporation. ~ther 1~ colorle~ or lightly colored aromatic polyisoc~yanates can similarly ~e used. Aromatic polyi.socyanate.s which might be color~e~s and, therefore, useful in the present invention include 2,4- and 2,6-hexahydrotolylene diisocyanate, hexahydro-1,3- and/or -4,4'-diphenyl methane dii~ocyanate, lS 1,3- and. 1,4-phenylene diisocyanate, ~,4- and 2,6-tolylene dii~ocyana~e, and naphthalene-1,5-diisocyanate.
The aliphatic polyisocyanate should be presen~ in an amount o~ about 50-100~ by welght based on the total wei~ht of polyiQocyantes in part B. Prefer~bly, the ~0 aliphatic polyisocyanate is present in an amount of about 40-90~ by weight, and more preferabl.y 70-80% by weight.
The aroma.ic p-lyisoc~anate shou]d be present in an amount of about 0-5~% by weight based on the total wei~ht of polyisocy~nates in part s Preferably, the aromatic polyisocyanate is present in an amount o~ about 5.0-40~ by weight, and more preferabl.y 10-20~ by weight.
Part A and/or Part B can contain a cataly~t nr a mixture of catalysts capable of acceleratin~ the cure rate of the polyurethane forming system. Desirably, the two-part polyurethane formin~ system cures in sufficient timeto be considered a fast cure polyurethane Any catalyst capa~le of a.ccele~ating the reaction rate between isocyanates and alcohols can be u~ed in the present invention. Preferably, the catalys~ i5 capable of accelerating the reactio~ between aliphatic and/or cycloaliphatic polyisocyanates and polyols. Exemplary catalysts are described in Squiller et al., ~Catalysis In Aliphatic Isocyanate-Alcohol Reactions," Modern Paint And C~atings, June 1987. Such catalyst~ include stannous octoate, dibutyltin dilaurate, manganese octoate, 7irconium octoate, cobalt octoate, lead octoate, bismuth stannate, lead stannate, zirconium octoate, zinc octoate, dih~tyltin bis-O-phenylphenate, di.butyltin S,S-dibutyldithio-carbonate, triphenylantimony dichloride, dibutyltin maleate, stannous oxala~e, s~annous stearate, barium nitra~e, cadmium octoate, dibutyltin diacetate, dibutyltin dilauryl mercaptide, DABCO catalyst, DBTDL and DAB~O
catalyst, ~ismuth stearate, lead stearate, dimethyltin dichloride, stannous na~thenate and m~xtuxes thereof.
Dibutyltin dilaurate is a particulaxly preferred catalyst for use in the p~esent inventi.on because o~ its reliability ~0 for ca~alyzing pol~urethanes.
The catalyst component i9 preferably incorporated into parl: A sinc~ the pol~als are rela~iv~ly u~rea~t.i.ve un~il mixed with the polyisocyanate. The catalyst could be incorporated in~o part R but may ha~e a tendency to accelerate the reaction between the isocyanate group6 and atmospheric o~ trace water. ~enera7ly, the catalyst is i~corporated into part A and/or part B i.n an amount sufficient to provide desired cat~lytlc activity. One skilLed in the art would readily appreciate the amount of catalyst necessary to provide catalyti.c activity.
Gene~ally, the catalyst should be present in an amount 219372~
ranging from 0.3-10~ by weight based on the total weight of the reacting ~omponellts.
A high pressure pump lubricant can a~ditiona~ly he incorpo~ated into part A and/or part B. Any known p~p lubrican~ can be used, including phosphates. A
particularly preferred lubricant is tricresyl pho,spha~e sold under the tradename KRONITEX TCP by F~M ~orp.
Surprisingly, when this pump lubricant is incorporated into part B, it additionally acts as an anti-moisture agent thereby extending ~he pot life ~f part B. Although no~
in~ending to be b~und by theory, i~ is believed that the vap~r pres-~ure o f this a~nt creates a gas barrier over the polyisocyanates in part B ~herehy xetarding access the~eto by atmospheric moisture. Certainly, other pot life ext~;n~ agents can be incorporated therein. Generally, the lubricant should be present in an amount ran~ing from about 0.1-5.0~ by weight based on the total welght of t;he polyi~ocyantes in part B.
A heat dissipating additiv~ can additi~nal~y ~e incorporated int~ part A and/o~ part B. Usually, it is easie~ to incorpvrate it in~o part A since par~ A is mo~e stable. The hea~ d~ssip~ting additive can be any inert diluent. When used in part A, it ~an additionally provide compatibility between the polyol ~omponents. Pre~erably, the heat dissipating agent i~ a chlorin~ted aliphatic hydrocarbon resin such ac, for example, C~LOROWAX 50 (chlorinated paraffinic plasticize~, chlori.ne content 48 wt. %, molecular weight 635), CHLOROWAX 60-70 (chlorinated paraffinic plasticizer, chlorine c~ntent 60 wt. ~), and ~H~OROWAX LV tParaffinic plastici.zer, chlorine contsnt 39 wt. ~, molecular weight 545). Generally, the heat dissipating additive should be present in an amount ranging - - 21937~0 from about 1. 0-20 . 0% by weight based on the total weight of the reac t ing component s in the s tr iping compos i t ion .
It is preferrecl fo.r traf f .ie-marking purposes (particularly highway marking) that striping compositions of this inve~tion either contain or be co~bined with a re~lectorizing fi.ller such as gla~s or plastic ~ead~ or bubbles. 'rhe reflectorizing filler is u~ed to provide i~creas~ retroreflecti~it~, particularly at night. I~he preferred reflectorizing additive are smoothf xound, ~ransparent glass spheres (e.g. beads), ~ubstantially free of milkiness, film scratch, pits, and air huhbles.
Preferably, not more than 30% o~ the beads are ovate or imper f ec t .
It presently appears that the most ef~ective application of the reflectorizin~ filler i~ to treat it as a third part ~part C) which can be added to the part A/part B system before or after it ha~ ~een appLi.ed to a road or highway surface. Generally, the reflectorizing flller i~
dropped onto the applied ~triping ccmpositio~ a~d become embedded therein Accordingly, it is desireable for the stripin~ compo~ition to have ~n open time sufficient to ~_ceive the reflectorizing filler. A less effective manner of incorporating the reflectorizing filler i.nto the part A~part B sys~em is to mi.x them into the part AJp~r~
mixture before it is applied to the road or highway surface. This lat~er app~oach is particularly undesirable if the reflectorizing ~iller is beads or hubbles which are easily fractured in a mixing step or if mixing is othe~wise made more complic~ted by, for example, abrading the appl$cation equipment. The amount of reflectorizing filler to be incorporated into the striping compo~ition can easi.ly be determined by one skilled in the art based ~Ipon the 1~
219372i) desired degree of retroreflectivity and on the type of re~lectorizing filler ~eing used. ~enerally, the reflectorizing ~i.ller should be ~resent in an amount ranging from 10-98% hy weigh.t of the total weigh.t of the S striping composition. Preferably, it ~ 9 present in an amount ran.~ing from 40-80~ by weight of the total. weight of the filler.
The two-part polyurethane forming system can contain additional componen~s known in the art, .if de.~i~ed.
Such additional components include, for example, diluents, pigments, plastici~ers, leveling agents, surfactants, fillers, additi~es and the ~ike. An exempl~y pigment includes titanium dioxide which can be used a.s a whi.tener.
Formulati~
Part A and part B are preferably comb;ned prior to application to a road or highway su~face. F~r example, parts A and ~ can be mixed in any commercial in-line static mixer or auger whi~h are well known in ~he art. It is believed. Graco Inc. manufactures e~Jipmen~ wh.ich can proce~s the striping composition of the present invention.
When applied to a road or highway ~urface, the striping composition can ~e applied in an~ desired thickness~ The minimum thickness should be enough to provide a~equate adhesion to the r~ad or highway surface and ~ufficient ~5 visibility. The ~aximum thickness is determined according to economic considerations taking into account the cost of the starting material~ and the potential increa~e in curing time to a thicker ~i.lm to cure. Prefe~abl~, the film thickness is between about 1 to 100 mils ~0..025 - 2.5 mm~
and more preferabl~ 5-'25 mils, depending upon the amount of re~1ectorizin~ fil~er incorporated therein. Most '~ cammercial application will provide a film th~ckne~s of ahout 10-15 mils.
The two-part s~riping composition preferably has a short pot life at room temperature (75~Fl. Pre~erably, the pot li~e is less than about 4 minutes and more prefera~ly less than about 1 minute. The pot life can be reduced by incorporating a hi.gher percentaae of aromatic polyisocyanate, using a different or greater amount of catalyst, heating or combinations thereo~ Certainly, ~he rate of reaction between polyisocyanates and polyols additionally depends on the partlcu~ar components u~ed in the reaction in terms of the reactivities of the components, steric hinderance, etc., which would be understood by one skilled in the art.
The stripin~ composition can be applied at room temperature. Alternati~ely, one or both parts can be heated prior to use to provide better flow properti.e~ and a f~ster cure time. P~eferably, the ~wo-part polyurethane forming system is heated to a temperature in the range 80-200~F prior to application. More preferably, it is heated to a temperature in the range o~ 100-150~F.
The ratio o~ part A t~ part ~ ~s ~refer2bly near 1:1 by vol~me, for example, between 0.9-7:1 and 1.05:1. One having skill in the art will readily appreciate that the proporti~n of par~ A to part B can be altered while ~taying within the spirit of the in~ention. It is desireable to have a slight excess of isocyanate groups. An excess of isocyanate groups of 1.05% is preferable in order to ensure that all of the hydroxyl groups o~ part A react. Exce5 iso~yanate ~roups can usually react with water.
The resulting cured striping composition can be a thermoset and have a shore-D hardness of at least about 60, 219372~
'~ and more preferably at least about 75. The max.im~ sh~r~-D
hardness should be l00, and is preferably less than 90. If the striping composition is too hard, it becomes brittle.
At lower harness level~, th~ striping composition wil.l pick 5 up dirt to easily. Thus, the striping composition is advantageous because it resi.sts dirt and retains flexibility. The striping compo~ition should ha~e a high tensile s~rength and compression strength which allows it ~o take ~t least l0,000 psi. In addition, it should have suff}cient abrasion resistance which allows it to withstand at least l,000 cycles from a ~S 17 wheel Tabor abrader, and pre~erably at least 50,00~ cycles.
The invention ~ill be further described wi.th reference to the following speci~ic examples which are not intended to limit ~he scope of inve~tion.
Exa~le 1 The following f~xmulation in Table ~. illustrates a two-part polyurethane formin~ syfitem according to the pre~ent invention. Part A and part B were mixed together in a ratio of l:l by ~olume. The re~ulting mixture had a pot life ~f approY.imat~ly one minute at 75~P.
Table l Part A Parts bv Weiqht ~OW RESIN 5~5 70.0 tripropylene glycol 30.
titanium dioxide 29.
~HLO~OWAX LV ll.l dibutyltin dilaura~e 04.0 - Par~ B Parts bY Weiqht DE~MODUR N-3300 114 . C~
LUPR~NATE MP102 36 . O
tr.icresyl phosphate 1. 4 The ma~erials i.dentified above hy tradem~rk have, accordiny to their suppliers, the following chemical composit~ons.
~DOW RESIN 565": diether of propylene glycol and bisphenol A (the hydroxyl ~roups being ~econdary, ava.ila~le from Dow ~hemical Company).
ProPertY Value hydroxyl e~livalent weight 175-185 viscosity ( 60~C) ~0~-1700 cp~
phenolic OH 0.02~ mc~.
col.or, Gardner 5.0 max.
pounds~gallons t2S~C~ g.2 density (80~/4~C) 1.069 "CHLOROWAX LV": liquid chlorinated para~fin, l~olecular weight 54S.0 ~available from Occidental Chemical Corporation).
"DESMODUR N-3300": aliphatic poly.isocyanate ~available from M-.le~ Inc. Coating Divi¢ion) " LUPRANATE MP10~": 4,~ diphenyl methane diisocyanate (available from sAs~ Corp. Polymers Division).
Exam~le 2, P~rt A and part B described in Example 1 w~re applied t~ a r~ad surfAce by spray application in a ratio of 1:1 by volume. The resulting film was white and cured sufficiently quickly ~i.e., about 30 ~econ.ds) so that coning was not necessary. The cured ~tripin~ composition adhered well t~ both asphalt and concrete ~urf~ces, and - should have a shore-D hardness in excess of 75 and not significantly yellow over time.
Exam~le 3 The process of example 1 was repeated and glass beads were dropped ont~ thc combined stripin~ composition before it cured, and became imbedded ~herein. The striping composition would be very reflective at night. ~he striping composition adhered well to both asphalt and 1~ ~onc~ete surfaces.
~xa~ple 4 A striping composition accordi~g to the present invention can be prepared ha~ing the ~ormulation ldentified in Table 2, wherein parts A and s can be mixed ~ogether ;.n a ratio of 1 0:1.05 by volL~e.
Tab.Le 2 Part A . Parts b~,r Weiqht DOW RESIN 565 9() . O
20 tripropylene glycol l() . O
titanium di.oxide 29.0 CHLClROWAX LV l 1 dibutyltin dilaurate 04.0 25 Part B Parts by Weiqht DESMO~UR N-3300 60.0 LUPRANATE MP10~ 40.0 tricresyl phofipha~e 1.4 ~x~mDl~ 5 A striping com~?ositiorl ac~cordi.ns~ to the present invention ~an be prepared ha~ing the formulation identified 2 937~0 , in Table ~, wherein pa~ts A and B can be mixed together in a ratio o~ 0. 97 :1 by volume.
Table 3 Part A Parts h~r Weiqht ~aw RESI~ 565 30. 0 tripropylene glycol. 70 . 0 ~ i tanium diaxide 2 9 . O
CHLOROWAX J.V 1 1.1 dibutyltin di.lau~ate 04 . 0 Part B Parts bY Weiqh~
DESMO~UR N-3300 90.O
LUPRANAT~ MP102 10.0 tricre~yl pho~p~ate 1.4
polyhydric alcohols such as glycerol and propylene glycol or polyfunctional compounds such a~ ethylene diamine a~d ethanolamine; epoxy resins of no~olak type, ~-methylepichloro type, cyclooxirane t~pe, gl.ycidyl ethertype, glycidyl ester type, gl.ycoL ether ~xpe, epoxylated unsaturated fatty acid type, epoxylated fatty acid ester -type, polybasic ca.rhoxylic acid ester type, amino-glycidyl type, halogenated type and resorcino] type; and monosaccharides or derivatives thereo~ .selected from fructose, glucose, ~ccharo.se, lac~ose or 2-S methylglucoxide.
For most applications, howe~er, p~lyols containingester groups are not preferred becau~e they tend to hydrolyze in the presence of alkaline present on road surface~. Un~aturation also tends to hydro3ize in the presence of alkaline. If de.sired, polyester~ and polyacrylates or other unsa~urated polymers can be used.
Such polymers are well known in the art.
Part A prefe~abl~ contains a mixture of a secondary diether dîol ~nd a lower polyalkylene glycol 15 component. A lower po~yalkylene glycol is meant to include polymers of glycols wherein the glycols have 2 - 10 carbon atoms. The second.ary diether diol provide~ the backbone for the stripin~ composition and i~ preferably a diether of propylene glycol and bisphen~l A ~hich is comme~cially av~ilabl.e under the tradem~rk DOW RESIN 5~5, a product of Dow Chemical ('o The lower po].ya.lkylene glycol i.s pr~'erably tripropylene glycol. 'Tlhe ~econda~y diether diol is preferably pre~ent in an amount ranging from about 30-90% by weight ~ased on the total. reactant weight in part A, and more preferably about 50-80~ by weight. At ~reater amounts o~ this component, the st~ipi~g composition becomes too soft. ~he ].ower alk~le~ glycol can be present in an amount ranging from 10-'70~ by weight based on the to~al reac~ant weight in part A, and more preferably about 20-40 by ~eigh~. At greater amounts o~ this component, the striping compo~ition becomes too brittle -- T~e Part B S~ t~L
This inventi~n contempla~es ~he use of an i~ocy~nate group-co~taining component ~part B) ca.pable of reacting with the isocyanate-reactive group-contAinin.
component~ contained in part A to provide a fast cure st~iping composition. The isocyanate group-containin~
component (part ~) preferably contains polyisocyana~es having a sufficient visc06ity which will allow part s to ~e processed through road striping apparatus without the use of solvents. The poly~socyanates should he capable of re~ctin~ with ~he polyols in part A to form a pol~lrethane system which will not significantly amber over time.
Aliphatic ~nd cycloalipha~ic polyiso~yanate are preferably used in part B because they tend to produce polyurethanes having decreased ambering. Generall~, aliphatic and cyclo~liphatic polyisocyanates whi.ch can be used in the pre~ent invention correspo~d to the formula Q ( NCO ) n in which n is an integer 2 to 4, and Q repre~ents an aliphatic hydrocarbon radical contain~n~ ~om 2 to 100 carbon atoms, and 7.ero to 50 heteroatoms, or a ~ycloaliphatic hydrccarbon radical coQtaining ~rom 4 to 100 carbon atoms and zero to 5() heter~atom~. Examples of alip~a~ic and cycloaliphatic polyisocyanates incl~de e~hylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, trimethy].h~xamethylene dii90cyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-l,3- and -1,4-dii.socyanate ~nd mixture of thos~ isomers, and l-isocyana~e-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane. Prefe.rred aliphatic and cycloaliphatic polyisocyanates are hexamethylene diisocyana~e, its isocyanurate an~ .its biuret a.nd ~.-~.0 219~ 0 isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane (isophorone diisocyanate). More preferably, the polyisocyanate is trimeri~ed hexamethylene diisocyanate ~DI~, a trifunctional isocyanurate. A commercially av~ilable trimerized hexamethylene diisocyanate is sold under the trademark DESMODUR N-3300 by Miles, Ine.
l'he use of aliphatic or cycloali.phati~
polyisocyanates a~ the only isocyanate group-containi.n~
components in par~ B can produce a sy~tem having a viscosity which is too high ~or convenient use in con~ercial road striping equipment. Ac~ording to the present inventio~, it is possible to replace part of the aliphatic or cycloaliphatic polyisocyanate with an aromatic polyisocyanate. Aromatic polyisocyanates can be useful because they tend to ~ve a viscosi~y decreasing effect when mixed with aliphatic or cycloaliphatic poLy~ocyanates and because they tend to react quickly. In addition, aromatic polyisocyanates tend to provide a faster reaction time and a harder finish. Aliphatic iso~yanates tend to a ~0 p~oduce softer polyure~hane but are more light stable.
Unfortunatel~, most aromatic polyisocyanates are brown and tend to produce yellow or bro~.~ polyurethanes. H~we~-er, by using an ar<~matic polyiso~yana~e which is colorless or on.ly very slightly colored, it is possible to produce a 2S polyurethane which retainS good amber r~ tant p~op~rties.
One skilled in the art wi~ 1 readily appreciate that the aro~atic polyisocyanate should be present in an ~mount suffici~nt to decrease the viscosity of part a $O it can be processed through road stripin~ e~ipment but within a 3V range ~ufficient to pre~ent signi~icant y~llowin~ or amberin~ of the xesulting polyurethane.
219~720 Diphenyl mel-hane d~isocyana~e ~e.g., diphenyl methane-2,4~- and/or -4,4'-diisocyanate~ is a prefer~ed aromatic polyisocyanate because it is ve~y lightly colored.
This aroma~ic polyisocyanate component i5 p~rticularly advantageous because when it is combined with trimerized hexamethylene diisocy~nate, a polyurethane resin can be produced which does not si~ni~icantly amber. Diphenyl methane diiso~yanate is commercially a~ail~ble lm der the trademark LUP~ANATE MP-~02 sold ~y RASF Corporation. ~ther 1~ colorle~ or lightly colored aromatic polyisoc~yanates can similarly ~e used. Aromatic polyi.socyanate.s which might be color~e~s and, therefore, useful in the present invention include 2,4- and 2,6-hexahydrotolylene diisocyanate, hexahydro-1,3- and/or -4,4'-diphenyl methane dii~ocyanate, lS 1,3- and. 1,4-phenylene diisocyanate, ~,4- and 2,6-tolylene dii~ocyana~e, and naphthalene-1,5-diisocyanate.
The aliphatic polyisocyanate should be presen~ in an amount o~ about 50-100~ by welght based on the total wei~ht of polyiQocyantes in part B. Prefer~bly, the ~0 aliphatic polyisocyanate is present in an amount of about 40-90~ by weight, and more preferabl.y 70-80% by weight.
The aroma.ic p-lyisoc~anate shou]d be present in an amount of about 0-5~% by weight based on the total wei~ht of polyisocy~nates in part s Preferably, the aromatic polyisocyanate is present in an amount o~ about 5.0-40~ by weight, and more preferabl.y 10-20~ by weight.
Part A and/or Part B can contain a cataly~t nr a mixture of catalysts capable of acceleratin~ the cure rate of the polyurethane forming system. Desirably, the two-part polyurethane formin~ system cures in sufficient timeto be considered a fast cure polyurethane Any catalyst capa~le of a.ccele~ating the reaction rate between isocyanates and alcohols can be u~ed in the present invention. Preferably, the catalys~ i5 capable of accelerating the reactio~ between aliphatic and/or cycloaliphatic polyisocyanates and polyols. Exemplary catalysts are described in Squiller et al., ~Catalysis In Aliphatic Isocyanate-Alcohol Reactions," Modern Paint And C~atings, June 1987. Such catalyst~ include stannous octoate, dibutyltin dilaurate, manganese octoate, 7irconium octoate, cobalt octoate, lead octoate, bismuth stannate, lead stannate, zirconium octoate, zinc octoate, dih~tyltin bis-O-phenylphenate, di.butyltin S,S-dibutyldithio-carbonate, triphenylantimony dichloride, dibutyltin maleate, stannous oxala~e, s~annous stearate, barium nitra~e, cadmium octoate, dibutyltin diacetate, dibutyltin dilauryl mercaptide, DABCO catalyst, DBTDL and DAB~O
catalyst, ~ismuth stearate, lead stearate, dimethyltin dichloride, stannous na~thenate and m~xtuxes thereof.
Dibutyltin dilaurate is a particulaxly preferred catalyst for use in the p~esent inventi.on because o~ its reliability ~0 for ca~alyzing pol~urethanes.
The catalyst component i9 preferably incorporated into parl: A sinc~ the pol~als are rela~iv~ly u~rea~t.i.ve un~il mixed with the polyisocyanate. The catalyst could be incorporated in~o part R but may ha~e a tendency to accelerate the reaction between the isocyanate group6 and atmospheric o~ trace water. ~enera7ly, the catalyst is i~corporated into part A and/or part B i.n an amount sufficient to provide desired cat~lytlc activity. One skilLed in the art would readily appreciate the amount of catalyst necessary to provide catalyti.c activity.
Gene~ally, the catalyst should be present in an amount 219372~
ranging from 0.3-10~ by weight based on the total weight of the reacting ~omponellts.
A high pressure pump lubricant can a~ditiona~ly he incorpo~ated into part A and/or part B. Any known p~p lubrican~ can be used, including phosphates. A
particularly preferred lubricant is tricresyl pho,spha~e sold under the tradename KRONITEX TCP by F~M ~orp.
Surprisingly, when this pump lubricant is incorporated into part B, it additionally acts as an anti-moisture agent thereby extending ~he pot life ~f part B. Although no~
in~ending to be b~und by theory, i~ is believed that the vap~r pres-~ure o f this a~nt creates a gas barrier over the polyisocyanates in part B ~herehy xetarding access the~eto by atmospheric moisture. Certainly, other pot life ext~;n~ agents can be incorporated therein. Generally, the lubricant should be present in an amount ran~ing from about 0.1-5.0~ by weight based on the total welght of t;he polyi~ocyantes in part B.
A heat dissipating additiv~ can additi~nal~y ~e incorporated int~ part A and/o~ part B. Usually, it is easie~ to incorpvrate it in~o part A since par~ A is mo~e stable. The hea~ d~ssip~ting additive can be any inert diluent. When used in part A, it ~an additionally provide compatibility between the polyol ~omponents. Pre~erably, the heat dissipating agent i~ a chlorin~ted aliphatic hydrocarbon resin such ac, for example, C~LOROWAX 50 (chlorinated paraffinic plasticize~, chlori.ne content 48 wt. %, molecular weight 635), CHLOROWAX 60-70 (chlorinated paraffinic plasticizer, chlorine c~ntent 60 wt. ~), and ~H~OROWAX LV tParaffinic plastici.zer, chlorine contsnt 39 wt. ~, molecular weight 545). Generally, the heat dissipating additive should be present in an amount ranging - - 21937~0 from about 1. 0-20 . 0% by weight based on the total weight of the reac t ing component s in the s tr iping compos i t ion .
It is preferrecl fo.r traf f .ie-marking purposes (particularly highway marking) that striping compositions of this inve~tion either contain or be co~bined with a re~lectorizing fi.ller such as gla~s or plastic ~ead~ or bubbles. 'rhe reflectorizing filler is u~ed to provide i~creas~ retroreflecti~it~, particularly at night. I~he preferred reflectorizing additive are smoothf xound, ~ransparent glass spheres (e.g. beads), ~ubstantially free of milkiness, film scratch, pits, and air huhbles.
Preferably, not more than 30% o~ the beads are ovate or imper f ec t .
It presently appears that the most ef~ective application of the reflectorizin~ filler i~ to treat it as a third part ~part C) which can be added to the part A/part B system before or after it ha~ ~een appLi.ed to a road or highway surface. Generally, the reflectorizing flller i~
dropped onto the applied ~triping ccmpositio~ a~d become embedded therein Accordingly, it is desireable for the stripin~ compo~ition to have ~n open time sufficient to ~_ceive the reflectorizing filler. A less effective manner of incorporating the reflectorizing filler i.nto the part A~part B sys~em is to mi.x them into the part AJp~r~
mixture before it is applied to the road or highway surface. This lat~er app~oach is particularly undesirable if the reflectorizing ~iller is beads or hubbles which are easily fractured in a mixing step or if mixing is othe~wise made more complic~ted by, for example, abrading the appl$cation equipment. The amount of reflectorizing filler to be incorporated into the striping compo~ition can easi.ly be determined by one skilled in the art based ~Ipon the 1~
219372i) desired degree of retroreflectivity and on the type of re~lectorizing filler ~eing used. ~enerally, the reflectorizing ~i.ller should be ~resent in an amount ranging from 10-98% hy weigh.t of the total weigh.t of the S striping composition. Preferably, it ~ 9 present in an amount ran.~ing from 40-80~ by weight of the total. weight of the filler.
The two-part polyurethane forming system can contain additional componen~s known in the art, .if de.~i~ed.
Such additional components include, for example, diluents, pigments, plastici~ers, leveling agents, surfactants, fillers, additi~es and the ~ike. An exempl~y pigment includes titanium dioxide which can be used a.s a whi.tener.
Formulati~
Part A and part B are preferably comb;ned prior to application to a road or highway su~face. F~r example, parts A and ~ can be mixed in any commercial in-line static mixer or auger whi~h are well known in ~he art. It is believed. Graco Inc. manufactures e~Jipmen~ wh.ich can proce~s the striping composition of the present invention.
When applied to a road or highway ~urface, the striping composition can ~e applied in an~ desired thickness~ The minimum thickness should be enough to provide a~equate adhesion to the r~ad or highway surface and ~ufficient ~5 visibility. The ~aximum thickness is determined according to economic considerations taking into account the cost of the starting material~ and the potential increa~e in curing time to a thicker ~i.lm to cure. Prefe~abl~, the film thickness is between about 1 to 100 mils ~0..025 - 2.5 mm~
and more preferabl~ 5-'25 mils, depending upon the amount of re~1ectorizin~ fil~er incorporated therein. Most '~ cammercial application will provide a film th~ckne~s of ahout 10-15 mils.
The two-part s~riping composition preferably has a short pot life at room temperature (75~Fl. Pre~erably, the pot li~e is less than about 4 minutes and more prefera~ly less than about 1 minute. The pot life can be reduced by incorporating a hi.gher percentaae of aromatic polyisocyanate, using a different or greater amount of catalyst, heating or combinations thereo~ Certainly, ~he rate of reaction between polyisocyanates and polyols additionally depends on the partlcu~ar components u~ed in the reaction in terms of the reactivities of the components, steric hinderance, etc., which would be understood by one skilled in the art.
The stripin~ composition can be applied at room temperature. Alternati~ely, one or both parts can be heated prior to use to provide better flow properti.e~ and a f~ster cure time. P~eferably, the ~wo-part polyurethane forming system is heated to a temperature in the range 80-200~F prior to application. More preferably, it is heated to a temperature in the range o~ 100-150~F.
The ratio o~ part A t~ part ~ ~s ~refer2bly near 1:1 by vol~me, for example, between 0.9-7:1 and 1.05:1. One having skill in the art will readily appreciate that the proporti~n of par~ A to part B can be altered while ~taying within the spirit of the in~ention. It is desireable to have a slight excess of isocyanate groups. An excess of isocyanate groups of 1.05% is preferable in order to ensure that all of the hydroxyl groups o~ part A react. Exce5 iso~yanate ~roups can usually react with water.
The resulting cured striping composition can be a thermoset and have a shore-D hardness of at least about 60, 219372~
'~ and more preferably at least about 75. The max.im~ sh~r~-D
hardness should be l00, and is preferably less than 90. If the striping composition is too hard, it becomes brittle.
At lower harness level~, th~ striping composition wil.l pick 5 up dirt to easily. Thus, the striping composition is advantageous because it resi.sts dirt and retains flexibility. The striping compo~ition should ha~e a high tensile s~rength and compression strength which allows it ~o take ~t least l0,000 psi. In addition, it should have suff}cient abrasion resistance which allows it to withstand at least l,000 cycles from a ~S 17 wheel Tabor abrader, and pre~erably at least 50,00~ cycles.
The invention ~ill be further described wi.th reference to the following speci~ic examples which are not intended to limit ~he scope of inve~tion.
Exa~le 1 The following f~xmulation in Table ~. illustrates a two-part polyurethane formin~ syfitem according to the pre~ent invention. Part A and part B were mixed together in a ratio of l:l by ~olume. The re~ulting mixture had a pot life ~f approY.imat~ly one minute at 75~P.
Table l Part A Parts bv Weiqht ~OW RESIN 5~5 70.0 tripropylene glycol 30.
titanium dioxide 29.
~HLO~OWAX LV ll.l dibutyltin dilaura~e 04.0 - Par~ B Parts bY Weiqht DE~MODUR N-3300 114 . C~
LUPR~NATE MP102 36 . O
tr.icresyl phosphate 1. 4 The ma~erials i.dentified above hy tradem~rk have, accordiny to their suppliers, the following chemical composit~ons.
~DOW RESIN 565": diether of propylene glycol and bisphenol A (the hydroxyl ~roups being ~econdary, ava.ila~le from Dow ~hemical Company).
ProPertY Value hydroxyl e~livalent weight 175-185 viscosity ( 60~C) ~0~-1700 cp~
phenolic OH 0.02~ mc~.
col.or, Gardner 5.0 max.
pounds~gallons t2S~C~ g.2 density (80~/4~C) 1.069 "CHLOROWAX LV": liquid chlorinated para~fin, l~olecular weight 54S.0 ~available from Occidental Chemical Corporation).
"DESMODUR N-3300": aliphatic poly.isocyanate ~available from M-.le~ Inc. Coating Divi¢ion) " LUPRANATE MP10~": 4,~ diphenyl methane diisocyanate (available from sAs~ Corp. Polymers Division).
Exam~le 2, P~rt A and part B described in Example 1 w~re applied t~ a r~ad surfAce by spray application in a ratio of 1:1 by volume. The resulting film was white and cured sufficiently quickly ~i.e., about 30 ~econ.ds) so that coning was not necessary. The cured ~tripin~ composition adhered well t~ both asphalt and concrete ~urf~ces, and - should have a shore-D hardness in excess of 75 and not significantly yellow over time.
Exam~le 3 The process of example 1 was repeated and glass beads were dropped ont~ thc combined stripin~ composition before it cured, and became imbedded ~herein. The striping composition would be very reflective at night. ~he striping composition adhered well to both asphalt and 1~ ~onc~ete surfaces.
~xa~ple 4 A striping composition accordi~g to the present invention can be prepared ha~ing the ~ormulation ldentified in Table 2, wherein parts A and s can be mixed ~ogether ;.n a ratio of 1 0:1.05 by volL~e.
Tab.Le 2 Part A . Parts b~,r Weiqht DOW RESIN 565 9() . O
20 tripropylene glycol l() . O
titanium di.oxide 29.0 CHLClROWAX LV l 1 dibutyltin dilaurate 04.0 25 Part B Parts by Weiqht DESMO~UR N-3300 60.0 LUPRANATE MP10~ 40.0 tricresyl phofipha~e 1.4 ~x~mDl~ 5 A striping com~?ositiorl ac~cordi.ns~ to the present invention ~an be prepared ha~ing the formulation identified 2 937~0 , in Table ~, wherein pa~ts A and B can be mixed together in a ratio o~ 0. 97 :1 by volume.
Table 3 Part A Parts h~r Weiqht ~aw RESI~ 565 30. 0 tripropylene glycol. 70 . 0 ~ i tanium diaxide 2 9 . O
CHLOROWAX J.V 1 1.1 dibutyltin di.lau~ate 04 . 0 Part B Parts bY Weiqh~
DESMO~UR N-3300 90.O
LUPRANAT~ MP102 10.0 tricre~yl pho~p~ate 1.4
3.5 It should be apparent to those skilled i~ the art that various changes may be made to this invention ~ithout departing from the spixit thereof, and that the inventi.on is not limited to what is described in the speci~icat.ion but only as indicated in the appended claims.
Claims (43)
1. A striping composition for use on a road or highway surface comprising a two-part polyurethane forming system having fast cure properties, said two-part polyurethane forming system comprising a first part containing isocyanate-reactive group-containing components and a second part containing isocyanate group-containing components, said striping composition being capable of curing to provide a no track film on a road or highway surface.
2. The striping composition according to claim 1, wherein said first part comprises a polyol selected from the group consisting of secondary diether polyols, alkylene glycols, polyalkylene glycols and mixtures thereof.
3. The striping composition according to claim 1, wherein said second part comprises an aliphatic polyisocyanate and an aromatic polyisocyanate.
4. The striping composition according to claim 3, wherein said aliphatic polyisocyanate is trimerized hexamethylene diisocyanate.
5. The striping composition according to claim 3, wherein said aromatic polyisocyanate is diphenyl methane diisocyanate.
6. The striping composition according to claim 2, wherein said polyol is a mixture of a secondary diether diol and a polyalkylene glycol.
7. The striping composition according to claim 6, wherein said diether is a diether of propylene glycol and bisphenol A.
8. The striping composition according to claim 2, wherein said polyalkylene glycol is tripropylene glycol.
9. The striping composition according to claim 1, wherein said second part further comprises a nonreactive high pressure pump lubricant capable of extending the pot life thereof compared with a second part not containing said nonreactive high pressure pump lubricant.
10. The striping composition according to claim 1, wherein said first part further comprises a catalyst and a heat dissipating additive.
11. The striping composition according to claim 1, wherein said composition will cure within four minutes after combining said first part and said second part, said cure takes place to an extent sufficient to prevent tracking thereof by ordinary highway traffic.
12. The striping composition according to claim 11, wherein said composition will cure within one minute after combining said first part and said second part.
13. The striping composition according to claim 1, said first part comprising:
Parts by Weight diether of propylene glycol and bisphenol A 70.0 tripropylene glycol 30.0 titanium dioxide 29.0 paraffinic plasticizer 11.1 dibutyltin dilaurate 04.0 said second part comprising:
Parts by Weight.
trimerized hexamethylene diisocyanate 114.0 diphenyl methane diisocyanate 36.0 tricresyl phosphate 1.4
Parts by Weight diether of propylene glycol and bisphenol A 70.0 tripropylene glycol 30.0 titanium dioxide 29.0 paraffinic plasticizer 11.1 dibutyltin dilaurate 04.0 said second part comprising:
Parts by Weight.
trimerized hexamethylene diisocyanate 114.0 diphenyl methane diisocyanate 36.0 tricresyl phosphate 1.4
14. A method for striping a road or highway surface, said method comprising the steps:
(a) combining a first part containing isocyanate reactive group containing components and a second part containing isocyanate group containing components to form a reacting striping composition free of essentially volatile solvents having a boiling point below l50°C at normal atmospheric pressure.
(b) applying said reacting striping composition to a road surface, (c) allowing said reacting striping composition to cure and adhere to said road surface.
(a) combining a first part containing isocyanate reactive group containing components and a second part containing isocyanate group containing components to form a reacting striping composition free of essentially volatile solvents having a boiling point below l50°C at normal atmospheric pressure.
(b) applying said reacting striping composition to a road surface, (c) allowing said reacting striping composition to cure and adhere to said road surface.
15. The method according to claim 14, wherein said combining step involves mixing.
16. The method according to claim 14, wherein said combining step involves spraying said first and second parts together.
17. The method according to claim 14, further comprising adding glass beads to said reacting striping composition to provide a striped road surface having retroreflectivity effect at night.
18. The method according to claim 14, wherein said first part comprises a polyol selected from the group consisting of secondary diether polyols, alkylene glycols, polyalkylene glycols and mixtures thereof.
19. The method according to claim 14, wherein said second part comprises an aliphatic polyisocyanate and an aromatic polyisocyanate.
20. A striped road prepared according to the process of claim 14.
21. The method according to claim l9, wherein said aliphatic polyisocyanate is trimerized hexamethylene diisocyanate.
22. The method according to claim 19, wherein said aromatic polyisocyanate is diphenyl methane diisocyanate.
23, The method according to claim 18, wherein said polyol is a mixture of a secondary diether diol and polyalkylene glycol.
24. The method according to claim 23, wherein said diether is a diether of propylene glycol and bisphenol A.
25. The method according to claim 14, wherein said polyalkylene glycol is tripropylene glycol.
26. The method according to claim 14, wherein the step of allowing said reacting striping composition to cure and adhere includes providing a no track time within four minutes after combining said first part and said second part, said cure takes place to an extent sufficient to prevent tracking thereof by ordinary highway traffic.
27. The method according to claim 14, wherein the step of allowing said reacting ,striping composition to cure and adhere includes providing a no track time within one minute after combining said first part and said second part.
28. The method according to claim 14, wherein said striping composition cures and adheres to said road surface to provide a shore-D hardness of between about 60 and about 100.
29. The method according to claim 28, wherein the shore-D hardness is between about 75 and about 90.
30. A striped road prepared by a method comprising the steps:
(a) combining a first part containing isocyanate reactive group containing components and a second part containing isocyanate group containing components to form a reacting striping composition free of essentially volatile solvents;
(b) applying said reacting striping composition to a road surface;
(c) allowing said reacting striping composition to cure and adhere to said road surface.
wherein said cured and adhered striping composition has a shore-D hardness of between about 60 and about 100.
(a) combining a first part containing isocyanate reactive group containing components and a second part containing isocyanate group containing components to form a reacting striping composition free of essentially volatile solvents;
(b) applying said reacting striping composition to a road surface;
(c) allowing said reacting striping composition to cure and adhere to said road surface.
wherein said cured and adhered striping composition has a shore-D hardness of between about 60 and about 100.
31. The striped road according to claim 30, wherein said cured and adhered striping composition has a shore-D
hardness of between about 75 and about 90.
hardness of between about 75 and about 90.
32. A method for applying a reactive composition to a concrete surface, said method comprising the steps:
(a) combining a first part containing isocyanate reactive group containing component and a second part comprising an isocyanate group containing component to form a reactive composition free essentially volatile solvents having a boiling point below 150°C at normal atmospheric pressure;
(b) applying said reactive composition to a concrete surface;
(c) allowing said reactive composition to cure and adhere to said concrete surface.
(a) combining a first part containing isocyanate reactive group containing component and a second part comprising an isocyanate group containing component to form a reactive composition free essentially volatile solvents having a boiling point below 150°C at normal atmospheric pressure;
(b) applying said reactive composition to a concrete surface;
(c) allowing said reactive composition to cure and adhere to said concrete surface.
33. The method according to claim 32, wherein said combining step comprises mixing.
34. The method according to claim 32, wherein said concrete surface comprises a pool structure.
35. The method according to claim 32, wherein said combining step comprises spraying said first and second parts together.
36. The method according to claim 32, wherein said first part comprises a polyol selected from the group consisting of secondary diether polyols, alkylene glycols, polyalkylene glycols, and mixtures thereof.
37. The method according to claim 32, wherein said second part comprises an aliphatic polylsocyanate and an aromatic polyisocyynate.
38. The method according to claim 32, wherein said composition will cure within four minutes after combining said first part and said second part.
39. The method according to claim 35, wherein said concrete surface comprises a road surface.
40. A construction comprising:
(a) an article comprising a concrete surface, and a reactive composition applied over the concrete surface, wherein said reactive composition comprises a mixture of a first part isocyanate reactive group containing component and a second part comprising an isocyanate group containing component, the reactive composition being free of essentially volatile solvent having a boiling point below 150°C at normal atmospheric pressure.
(a) an article comprising a concrete surface, and a reactive composition applied over the concrete surface, wherein said reactive composition comprises a mixture of a first part isocyanate reactive group containing component and a second part comprising an isocyanate group containing component, the reactive composition being free of essentially volatile solvent having a boiling point below 150°C at normal atmospheric pressure.
41. The construction according to claim 40, where the reactive composition adheres to the concrete surface.
42. The construction according to claim 40, wherein the article comprises a road.
43. The construction according to claim 40, wherein the article comprises a pool structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002193720A CA2193720A1 (en) | 1996-12-20 | 1996-12-20 | Striping composition and method for striping a road or highway surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002193720A CA2193720A1 (en) | 1996-12-20 | 1996-12-20 | Striping composition and method for striping a road or highway surface |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2193720A1 true CA2193720A1 (en) | 1998-06-20 |
Family
ID=4159508
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002193720A Abandoned CA2193720A1 (en) | 1996-12-20 | 1996-12-20 | Striping composition and method for striping a road or highway surface |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2193720A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2472474B (en) * | 2009-12-14 | 2012-04-11 | Pro Teq Surfacing Uk Ltd | Method for applying a coating to a surface |
-
1996
- 1996-12-20 CA CA002193720A patent/CA2193720A1/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2472474B (en) * | 2009-12-14 | 2012-04-11 | Pro Teq Surfacing Uk Ltd | Method for applying a coating to a surface |
| US9017769B2 (en) | 2009-12-14 | 2015-04-28 | Pro-Teq Surfacing (Uk) Ltd | Method and apparatus for applying a coating to a surface |
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