CA2180628A1 - Hockey stick blade having an abrasion resistant coating and process for coating said blade - Google Patents
Hockey stick blade having an abrasion resistant coating and process for coating said bladeInfo
- Publication number
- CA2180628A1 CA2180628A1 CA 2180628 CA2180628A CA2180628A1 CA 2180628 A1 CA2180628 A1 CA 2180628A1 CA 2180628 CA2180628 CA 2180628 CA 2180628 A CA2180628 A CA 2180628A CA 2180628 A1 CA2180628 A1 CA 2180628A1
- Authority
- CA
- Canada
- Prior art keywords
- coating
- blade
- diisocyanate
- mixture
- omega
- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B59/00—Bats, rackets, or the like, not covered by groups A63B49/00 - A63B57/00
- A63B59/70—Bats, rackets, or the like, not covered by groups A63B49/00 - A63B57/00 with bent or angled lower parts for hitting a ball on the ground, on an ice-covered surface, or in the air, e.g. for hockey or hurling
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B2102/00—Application of clubs, bats, rackets or the like to the sporting activity ; particular sports involving the use of balls and clubs, bats, rackets, or the like
- A63B2102/24—Ice hockey
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B2209/00—Characteristics of used materials
- A63B2209/02—Characteristics of used materials with reinforcing fibres, e.g. carbon, polyamide fibres
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Physical Education & Sports Medicine (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a hockey stick blade having an abrasion resistant coating to a hockey stick comprising such a blade and to a process for coating a hockey stick blade. The coating is made from polyurethane or a mixture of polyurethane and polyurea and has a durometer hardness of at least about 70A. In a preferred embodiment, the coating may be made by mixing a urethane prepolymer having isocyanate terminal groups with an amine component. The coating of the present invention is particularly useful on harsh surfaces such as roller hockey surfaces and allows a player to use a stick that possesses better feel while reducing friction and abrasion.
Description
-~' 2183~28 TITLE: HOCKEY STICK BLADE HAVING AN ABRASION RESISTANT
CQATING AND PROCESS FOR COATING SAID BLADE
FIELD OF THE INVENTION
The present invention relates to the field of hockey sticks and particularly to a hockey stick blade having improved wear properties. More particularly, the invention relates to a hockey stick blade cu" ", i~i"g an abrasion resistant coating.
BACKGROUND TO THE INVENTION
The recent rise in popularity of in-line roller skates for use in leisure sport has also found it way into the field of hockey, the sport being commonly referred to as "in-line hockey" or "roller hocker. Tl d~iliVI I ~Iy, hockey has been practised on an ice rink whose surface is smooth and very slippery. Unlike ice hockey however, the surface on which roller hockey is played is somewhat harsh and as a result, increases the abrasion and the wear of the blade of a hockey stick. The lldl ~ l ,e:,s of the surface also means that the blade should exert as liUle friction as possible so as to be able to "glide' more easily on the surface of play.
-~ 2lsa62s In order to overcome the problems ~co.,i~l~d with abrasion, hockey stick manufacturers have .s~ st~cl using stick blades made from various synthetic materials such as acrylonitrile-butadiene-styrene polymers (ABS) which are more resistant to wear. These hockey sticks have not hov~ever provided ~.~t;~rd-,lory results. Since traditional hockey sticks are constructed of wood, either alone or in cu" ,ui" ' , with various c~" I,uG~:;;'u.S such as fibreslass, carbon fibres or the like, they possess a certain feel to which hockey players have become accustomed. This "wood-like" feel is not present ir~ the co,~,ru.,lional ABS roller hockey stick. Thus, the player is left with two ~"c.. li~r~ y choices; either to play with a conventional hockey stick whichprovides the d~J,UI U,UI id~ feel but that is subject to accal~, dl~d wear of the blade or to play with a synthetic stick that is more resistant to abrasion but that does not possess the d,U,UI upridla feel.
In order to improve the wear properties of the blade, some manufacturers have also Cll~gQstpd using prepolymerized resins, such as phenoxy resins, dissolved in a volatile solvent such as a ketone. Other manufacturers have suggested using eld~lUI 11~ , coatings. These coatings llave however been u" ,.,l i~r~. jl, .ry for various reasons including, among others, their incapacity to resist wear over a relatively long period of time and their tendency to become brittle, i.e. their incapacity to deform before breaking when providedwith a hardness that is hi~h enough to adequately reduce friction. Yet another 2lsa~2s major disadvanta3e of using such coatings is the necessity to use organic solvents which are rather harmful to the env;.u"",t",I and which have other .~.so.,i,,l~d disadvantages.
There is thus a need for a hockey stick blade uO"~ i"s~ an abrasion resistant coating that will exhibit a level of hardness high enou~h to resist wear and adequately reduce friction without having a tendency to become brittle.
OBJECTS AND STATEMENT OF THE INVENTION
It is therefore an object of the present invention to provide a hockey stick blade which is more abrasion resistant than a conventional hockey stick blade.
A further object of the invention is to provide a hockey stick blade cu" ,,u, i~i"~ an abrasion resistant coating having a hardness sufficient to prevent accelc~ wear while adequately reducing friction.
As embodied and broadly described herein, the invention provides a hockey stick blade having a lower edge for contacting a surface of play, at least a portion of the lower edge bearing an abrasion resistant coating 2180~28 cu",~ ,i"g polyurethane, the coating having a durometer hardness of at least about 7ûA.
In a preferred ~",uodi",e"L, the coating comprises polyurethane and polyurea, and most preferably, the coating is made by mixing a urethane prepolymer having isocyanate terminal groups with an amine co",,uo,~
In one ~"luo.li,"~"l, the urethane prepolymer is made by reacting a mixture of toluene-2,4-diisocyanate and toluene-2,6-diisocyanate with an a,~
1 û glycol having between 2 and 6 carbon atoms, mixtures thereof or a low molecular weight polymer thereof and the amine co" ,,uo,~, ,l is a diamine which is mixed with an a,~-glycol having between 2 and 6 carbon atoms or mixtures thereof.
Most preferably, the urethane prepolymer is made by reacting a mixture of toluene-2,4-diisocyanate and toluene-2,6-diisocyanate with an a-hydro-~,)-hydroxypoly (oxy-1,4-butanediyl) and the amine co"",ùne"L is a mixtureof 4,4'-methylene dianiline with an a-hydro-lD-hydroxypoly [oxy(methyl-1,2-ethanediyl)].
2û As embodied and broadly described herein, the invention also provides a hockey stick blade having a lower edge for contacting a surface of ~ ~y, at le~st a port on of the lower ed~e bearing an abrasion resistant coating ~ ~80628 having a durometer hardness of at least about 70A, the coating being made by mixing a urethane prepolymer with an amine cu",uo"~"L, the urethane prepolymerbeing made by reacting an d,upluAillldl~ly 80:20 mixture of toluene-2,4-diisocyanate and toluene-2,6-diisocyanate with an d,U,UlUAilll..~ly 90:10 mixture of two a-hydro-ll)-hydroxypoly (oxy-1,4-butanediyls) having molecular weights of about 1000 and about 2000" ~,ue~t~ ,~cly, the amine c~" ,,uu"e"l being a mixture of 4,4-methylene dianiline with an du~,uA;",dLely 75:25 mixture of two a-hydro-l,)-hydroxypoly [oxy(methyl-1 ,2-ethanediyls)] having molecular welghts of about 1000 and about 500, respectively.
In another ~Illbodi~ l, the coating is made by mixillg a diisocyanate with an amine mixture cu",,uli~i"g an amine cu,,,,uol~ellll an a,~-glycol having between 2 and 6 carbon atoms, mixtures thereof or a low molecular weight polymer thereof. Preferably, the diisocyanate is diphenylmethane diisocyanate and the amine mixture comprises an a-hydro-(l)-hydroxypoly (oxy-1,4-butanediyl), 4,4'-methylene dianiline and an a-hydro~
hydroxypoly [oxy(methyl-1,2-ethanediyl)].
In a preferred ~"l~o~i",t,"~, the coating has a durometer hardness between about 70A and 75D.
o 218~628 Preferably, the ooating is between 20 to 30 mils thick and may comprise a pigment.
In another aspect, the invention also provides a hockey stick c~",~,isi"g a blade ooated in ac.,u,.ldl,-,e with the teachings of the present invention.
As embodied and broadly described herein, the invention also provides a prooess for ooating a hockey stick blade, the process comprising the step of applying to a blade a coating cu",,u,i:,;"3 polyurethane and having a durometer hardness of at least 7ûA, the prooess being carried out in the absenoeof or subsldl ,li~:'y in the absence of solvent.
In a preferred ~Illbodi~ , the prooess oomprises the steps of:
a) reacting a mixture of toluene-2,4-diisocyanate and toluene-2,6-diisocyanate with an a,(l)-glycol having between 2 and 6 carbon aloms, mixtures thereof or a low molecular weight polymer thereof to form a urethane prepolymer;
b) mixing a diamine with an a,o~-glyool havin3 between 2 and 6 carbon atoms or mixtures thereof to provide an amine c~" ~,u0~1~1 ,L, c) mixin3 the urethane prepolymer and the amine c~" ~,uol)el ,L to form a coatin3 uulll,uo~iLil)~l, and 2~80628 d) applying the cul "~osiliù" to the blade.
In a preferred ~" l~dil "e"l, the urethane prepolymer and the amine component are heated to a L~ e of about 70~C i 1~C before being admixed and applied to the blade.
Most preferably, the urethane prepolymer of step a) is made by reacting a mixture of toluenQ-2,4-diisocyanate and toluene-2,6-diisocyanate withan a-hydro~-hydroxypoly (oxy-1 ,4-butanediyl) and the amine cc l l ,pol1e~ ll of step b) is a mixture of 4,4'-methylene dianiline with an a-hydro-t~)-hydroxypoly [oxy(methyl-1,2 I,:I,anediyl)]. Preferably, the process is canried out in the absence of or suu~ldl lli~lly in the absence of solvent.
The blade coated in acculddllGe with the invention has the advantage of preventing a~eltndlt:d wear due to harsher playing surfaces while reducing friction. The inventor has also discovered that the coating of the present invention is advantageous when used on traditional ice hockey rinks.
Indeed, although ice surfaces are not as harsh as roller hockey surfaces, ice hockey stick blades are l1u~ eless subjected to abrasion. This condition should be avoided since as a result of the abrasion, water tends to penetrate inside the blade and reach the fibreglass, if any, thereby contributing to the cleld" ,i, l~liol~ of the cu" ,,uu"~"t~ of the stick which, over time, induces structural ~ ~180628 failure to the stick. This problem may be avoided by providing an ice hockey stick blade with the coating of the present invention.
Other objects and features of the invention will become apparent by reference to the following desu, i,uLiol~ of a preferred ~" Ibodi, "e"~.
DESCfi,. I ION OF A PREI LI~REu EMBODIMENT
The inventors have discovered that the objects of the present invention could be achieved by providing a coating having a durometer har~ness of at least about 70A when measured in accu, ~Ito ,~e with the ASTM D-2240 test.More precisely, the inventors have realized that a suitable coating having such properties may be obtained by using a cu" I,uOailiul ~ .u" lu(iail ,9 polyurethane or a mixture of polyurethane and polyurea.
In acc~"~ance with a preferred ~ uodi~ L of the invention, a coating is provided on the lower edge of the blade of a hockey stick. For the purpose of this , ~ ' ,, the e~, ~s~iu" "lower edgeD is intended to cover the portion of the blade that is in contact with a surface of play. The coating can be applied on the entire edge or simply on the area that contacts the surface of play such as, for example, the heel portion. Similarly, the blade could be pro\/ided ~ ~18~28 with a coating that is thicker at the heel portion and thinner at the front portion.
In yet another ~",I,o.li",e"~, the coating could be applied on the entire blade.
A coating according to a hrst ~ o.li~ l of the invention may consist of a polyurethane made by reacting an isocyanate and a polyol.
The isocyanate may be a diisocyanate or a triisocyanate. Suitable diisocyanates for use in preparing the coating of the present invention comprisepreferably a mixture of toluene-2,4-diisocyanate and toluene-2,6-diisocyanate and their derivatives. A preferred diisocyanate is an d~J~lU,~lllldl~ly ~0:20 mixture of toluene-2,4-diisocyanate and toluene-2,6-diisocyanate. Such a mixture is cu"""t~ available and is sold under the trademark MONDUR TD-80 (Product of Bayer). Other suitable diisocyanate include diphenylmethane diisocyanate, naphthylene diisocyanate, a,(,l-alkylene diisocyanates such as he,xd",t:l~,ylene diisocyanate and its derivatives an homologues. Suitable triisocyanates include triphenylmethane-pp'p" triyl triisocyanate.
Suitable polyhydroxy compounds (polyols) that react with the diisocyanates or triisocyanates include diols or triols. Amongst the suitable diols are a,l,~-glycols having between 2 and 6 carbon atoms or mixtures thereoF, the glycols being preferably straight chain. A most preferred diol is a-hydro-~
hydroxypoly (oxy-1 ,4-butanediyl) having a molecular weight of about 1000 or a g ~ 2180628 molecular weight of about 2000 or blends thereof. Such products are co"""e,N~ 'y available under the L,dd~",arks TERATHANE 1000 and 2000 (products of DuPont). The use of triols is also COIll~lllr 3~. Amongst the suitable triols are polyoxypropylene triols. However the use of triols may make it more difficult to control the properties of the coating u u" ~o~ iu~.
The coating of the pr~3sent invention may also comprise some of the additives that are commonly found in such c~" ,~.osilions. Amongst the additivesare pigments used to add colour to the coating. These pigments may be carbon black titanium dioxide or iron oxide and are usually added in an amount not ~xceedi"g 1%. The cu",uosiliu" may also comprise a slip agent cu",~.dli~le therewith to provide good slip properties to the coating. Examples of slip agents include fat~y acids derivatives such as oleamide. When present these agents are added in an amount not exceeding 0.1%. To prevent ~llu~u;ll~lllicdl dey, d~dliUI I and acc~31e, dled oxidation of the coating as a result of exposure to UV radiation there may also be provided a UV stabilizer. Both the choic~3 and the type of UV stabilizer may be d~ '~ lllill~d by the person skilled in the art.
Other additives such as hllers dl lliO~iddl IL~ 1 ,iche,le, ~ or emulsifiers may also be included in the cc " ,~,osilion.
The coating should be within the specified range since a coating having a durometer hardness below about 70A may be too soft and may not allow the player to benefit from the reduced friction. On the other hand the inventor has realized that a coating having a durometer hardness above about 75D may have a tendency to become brittle and as a result the durometer hardness of the coating should not exceed 75D. However the person skilled in the art will realize that the maximum value for the hardness may only depend on the desired: ,~ and this limitation should not be i"~, u, ~ in a llmiting manner.
The person skilled in the art will realize that it is possible to adjust the hardness of the coating by using various additives or by modifying the type of isocyanate or polyol so that the durometer hardness will fall within the scope of the present invention. Such Illo.liri.dliu~s may be d~ ~ .",i"ed by rcutine testing.
A coating according to a second e",L,o~i",e"L of the present invention comprises a mixture of polyurethane and polyurea and is made from mixing a urethane prepolymer with an amine c~" ,u~n~"~. It may also comprise further additives such as the ones previously " ,e, lliul ,ed.
The urethane prepolymer is prepared by reacting an isocyanate with a polyol as described in relation with the first ~",L)odi",e"L. The hydroxy~roupsofth=p It Iwillthusr=adwith~h= socy=ntt~egloupsot~hedilswanat=
218~628 to form a urethane prepolymer. However, unlike the first e",L,o~i",e"~ in vvhichthe coating comprises only polyurethane and additives, if any, the molar ratio of the polyol to the isocyanate is d~ " ,i"ed so that the urethane prepolymer will have isocyanate terminal groups, hence the use of the e,~y, ~:,SiO,l "prepolymer".
Preferably, the ratio of polyol to isocyanate is chosen so that there will be between 6% to 10% excess diisocyanate in the urethane prepolymer.
The isocyanate terminal groups of the urethane prepolymer are then mixed with an amine c~"~,uollel ,~ to form a coating co",,u~silion cu,"p, isi"g a mixture of polyurethane and polyurea.
The amine ~",,uu"~"~ is preferably a diamine. Suitable diarnines include a,~,~-alkyl~, n~ idl l lil ,e having preferably between 2 to 6 carbon atoms and aromatic diamines such as 4,4'-methylene bis(2-.,1,1u,ud, " ,e), 2,4-toluene diamine,diethyl or 4,4'-methylene dianiline.
While it is possible to mix the urethane prepolymer directly with the amine c~" ,,,~one"~, it is however preferable, for handling purposes, if the amine ~u,",uu"e"~ is mixed with a suitable glycol that acts as a chain extender. Thus,the amine cu,,,,uon~ may be a diamine mixed with an a,~-glycol having between 2 and 6 carbon atoms or mixtures thereof. Most preferably, the mixture is obtained by mixing equal amounts of 4,4'-methylene dianiline with an ~ ~180~28 app,u~i,,,dLely 75:25 mixture of two o:-hydro-("-hydroxypoly [oxy(methyl-12-e:llldl~ediyls)] having a molecular weight of about 1000 and about 500 respectively.
The person skilled in the art will realize that it may be possible to use other amine ~ ~" IpUI~ or mixtures provided that the a~ui~,l liO" It:LI iC ratio is adjusted to take into cu"~ide,dliol~ the variations in molecular weight.
Examples of other suitable amine Cu~pO~ include 4 4-methylene bis(2-~:1 llul Udl "' ,e) or 2 4-toluene diamine diethyl. Similarly other glycols such as a-hydro-~l)-hydroxypoly (oxy-1 4-butanediyl) could be used.
Additives such as the ones described in relation with the first e,,l~o~i,,,e"I may also be used.
The invention will be further u"~e, ~luod by the desu, i~iu" of the following example that co" ~t~s a preferred e"ILo~i,"e"l of the invention and that should not be construed in a limiting manner:
~ ~18~628 Example 1 COMPOSITION
I~.~,.. 'i~ It %bvweiaht Mixture A (urethane ~ pol~., ) MONDUR TD-80 ' ~30 TERATHANE 1000 and 2000 2 ~60 mixture B (amine ~ .u..- .~t and additives) 4,4'-methylene dianiline ~5 a-hydro-~t-hydroxypoly [oxy(methyl-1 ,2-ethanediyl)] 3 ~5 carbon black ~0.25 t a~ 80:20 mixture of toluene-2,4-diisocyanate and toluene-2~6~;icl~cy-~ ~
2 u~ so:1 o mix~ure of two ~-hydro ~ (oxy-1 ,4-butanediyls) having mol,ecular weights of about 1000 and about 2000, respec~tvely.
3 ~ 75 :25 mixture of two c~-hydro-~)-hydroxypoly loxy(methyl-1 ,2 .~ Itaving molecular weights of about 1000 and about soo, respectively.
The i"y" ~tdittl 1~ of mixture A were mixed to3ether in a first chamber andwereheatedtoatemperatureofabout70~Ci10~C. Similarly, the illyl~tdittllI:~
of mixture B, including any other additives, were mixed together in a second chamber and were also heated to a temperature of about 70~Ci1 0~C.
Mixtures A and B were then mixed together in a 2:1 ratio (two part mixture A and one part mixture B) and the resulting uu" ~,uO~iIiul ~ was applied to a wood hockey stick blade by using a spray gun. A PROBLER gun (Product of Glas-Craft) with a 17:1 fluid to air ratio was found to be suitable for this. The use of such a spray gun facilitates the coating operation since the two mixtures A and B are only mixed at the tip of the gun thereby preventing premature ' i~Iiu,, 2~8~628 of the c~" ,~.o ,it;." ,. In a variant, the tip of the spray gun may be removed and the cul~ " , may be applied as a bead. The person skilled in the art will however realize that the co",,u~a~ n may be applied to the blade using other similar equipment or other coating techniques known in the art. A prefenTed thickness for roller hockey is d,U,UI o,~i" Idl~ly from 10 to 50 mils and preferably from 20 to 30 mils but the thickness may vary according to the intended use. Also, the coatingmay be applied in a single ,, " " , or in a series of d,U~.)Ii~ d~iUl~s In the latter case however, each coating is not left to dry before the other coating is applied.
The c~,, ,,uosiliol~ was then left to dry under normal con.litions and solidified thereby providing an abrasion resistant coating. A period of between 40 to 60 seconds was found to be sufFicient to complete the drying.
PHYSICAL PROPERTIES
The coating of example 1 exhibited the following ~, u~ s.
Property Result Test 20 Hardness (durometerShore D) 50Di5D ' ASTM D-2240 Tensile strength (psi) 3200 ASTM D-412 Elongation (%) 300 ASTM D-412 Resiliency (%) 45 ASTM D-2632 This value is equivalent to a durometer hardness of at least 90A.
~ 2180628 The coating of example 1 was tested on pavement and on an ice rink and provided sdlibrduLury results.
While the coating of the second ~"ILJo.li,"~"L was prepared by a urethane prepolymer with an amine uu, I ,pu~ ,e"~, in yet a third ~" ,~ou'i" ,e"L, the coating could be prepared by mixing a diisocyanate with a mixture cu,,,p, isi, lg a polyol, an amine cu",,uo,~ and additives, if any. For apparent reasons, a less dangerous diisocyanate such as diphenylmethane diisocyanate should preferably be used in such an ~:IllL)odilllt:llt instead toluene-2,4-diisocyanat3 and 1 û toluene-2,6-diisocyanate.
Because of the relatively fast ' ' ~ " 1 time of the cc " I~ObitiOI 1, the use of the coating of the present invention may improve the efficiency of the manufacturing process of hockey stick blade thereby lowering costs.
Furthermore, the use of the coating according to the invention avoid the use of volatile organic compounds which might be released into the dll "~b,ulle, ~ and is thus safer for the environment.
The above desu,i,u~iu,~ of a preferred e",L)odi",~"l should not be 2û i, l~, ,u, ~l~d in any limiting manner since variations and, ~ri"~" ,e, ILb are possible which are within the spirit and scope of the present invention. The scope of theinvention is defined in the appended claims and their equivalents.
CQATING AND PROCESS FOR COATING SAID BLADE
FIELD OF THE INVENTION
The present invention relates to the field of hockey sticks and particularly to a hockey stick blade having improved wear properties. More particularly, the invention relates to a hockey stick blade cu" ", i~i"g an abrasion resistant coating.
BACKGROUND TO THE INVENTION
The recent rise in popularity of in-line roller skates for use in leisure sport has also found it way into the field of hockey, the sport being commonly referred to as "in-line hockey" or "roller hocker. Tl d~iliVI I ~Iy, hockey has been practised on an ice rink whose surface is smooth and very slippery. Unlike ice hockey however, the surface on which roller hockey is played is somewhat harsh and as a result, increases the abrasion and the wear of the blade of a hockey stick. The lldl ~ l ,e:,s of the surface also means that the blade should exert as liUle friction as possible so as to be able to "glide' more easily on the surface of play.
-~ 2lsa62s In order to overcome the problems ~co.,i~l~d with abrasion, hockey stick manufacturers have .s~ st~cl using stick blades made from various synthetic materials such as acrylonitrile-butadiene-styrene polymers (ABS) which are more resistant to wear. These hockey sticks have not hov~ever provided ~.~t;~rd-,lory results. Since traditional hockey sticks are constructed of wood, either alone or in cu" ,ui" ' , with various c~" I,uG~:;;'u.S such as fibreslass, carbon fibres or the like, they possess a certain feel to which hockey players have become accustomed. This "wood-like" feel is not present ir~ the co,~,ru.,lional ABS roller hockey stick. Thus, the player is left with two ~"c.. li~r~ y choices; either to play with a conventional hockey stick whichprovides the d~J,UI U,UI id~ feel but that is subject to accal~, dl~d wear of the blade or to play with a synthetic stick that is more resistant to abrasion but that does not possess the d,U,UI upridla feel.
In order to improve the wear properties of the blade, some manufacturers have also Cll~gQstpd using prepolymerized resins, such as phenoxy resins, dissolved in a volatile solvent such as a ketone. Other manufacturers have suggested using eld~lUI 11~ , coatings. These coatings llave however been u" ,.,l i~r~. jl, .ry for various reasons including, among others, their incapacity to resist wear over a relatively long period of time and their tendency to become brittle, i.e. their incapacity to deform before breaking when providedwith a hardness that is hi~h enough to adequately reduce friction. Yet another 2lsa~2s major disadvanta3e of using such coatings is the necessity to use organic solvents which are rather harmful to the env;.u"",t",I and which have other .~.so.,i,,l~d disadvantages.
There is thus a need for a hockey stick blade uO"~ i"s~ an abrasion resistant coating that will exhibit a level of hardness high enou~h to resist wear and adequately reduce friction without having a tendency to become brittle.
OBJECTS AND STATEMENT OF THE INVENTION
It is therefore an object of the present invention to provide a hockey stick blade which is more abrasion resistant than a conventional hockey stick blade.
A further object of the invention is to provide a hockey stick blade cu" ,,u, i~i"~ an abrasion resistant coating having a hardness sufficient to prevent accelc~ wear while adequately reducing friction.
As embodied and broadly described herein, the invention provides a hockey stick blade having a lower edge for contacting a surface of play, at least a portion of the lower edge bearing an abrasion resistant coating 2180~28 cu",~ ,i"g polyurethane, the coating having a durometer hardness of at least about 7ûA.
In a preferred ~",uodi",e"L, the coating comprises polyurethane and polyurea, and most preferably, the coating is made by mixing a urethane prepolymer having isocyanate terminal groups with an amine co",,uo,~
In one ~"luo.li,"~"l, the urethane prepolymer is made by reacting a mixture of toluene-2,4-diisocyanate and toluene-2,6-diisocyanate with an a,~
1 û glycol having between 2 and 6 carbon atoms, mixtures thereof or a low molecular weight polymer thereof and the amine co" ,,uo,~, ,l is a diamine which is mixed with an a,~-glycol having between 2 and 6 carbon atoms or mixtures thereof.
Most preferably, the urethane prepolymer is made by reacting a mixture of toluene-2,4-diisocyanate and toluene-2,6-diisocyanate with an a-hydro-~,)-hydroxypoly (oxy-1,4-butanediyl) and the amine co"",ùne"L is a mixtureof 4,4'-methylene dianiline with an a-hydro-lD-hydroxypoly [oxy(methyl-1,2-ethanediyl)].
2û As embodied and broadly described herein, the invention also provides a hockey stick blade having a lower edge for contacting a surface of ~ ~y, at le~st a port on of the lower ed~e bearing an abrasion resistant coating ~ ~80628 having a durometer hardness of at least about 70A, the coating being made by mixing a urethane prepolymer with an amine cu",uo"~"L, the urethane prepolymerbeing made by reacting an d,upluAillldl~ly 80:20 mixture of toluene-2,4-diisocyanate and toluene-2,6-diisocyanate with an d,U,UlUAilll..~ly 90:10 mixture of two a-hydro-ll)-hydroxypoly (oxy-1,4-butanediyls) having molecular weights of about 1000 and about 2000" ~,ue~t~ ,~cly, the amine c~" ,,uu"e"l being a mixture of 4,4-methylene dianiline with an du~,uA;",dLely 75:25 mixture of two a-hydro-l,)-hydroxypoly [oxy(methyl-1 ,2-ethanediyls)] having molecular welghts of about 1000 and about 500, respectively.
In another ~Illbodi~ l, the coating is made by mixillg a diisocyanate with an amine mixture cu",,uli~i"g an amine cu,,,,uol~ellll an a,~-glycol having between 2 and 6 carbon atoms, mixtures thereof or a low molecular weight polymer thereof. Preferably, the diisocyanate is diphenylmethane diisocyanate and the amine mixture comprises an a-hydro-(l)-hydroxypoly (oxy-1,4-butanediyl), 4,4'-methylene dianiline and an a-hydro~
hydroxypoly [oxy(methyl-1,2-ethanediyl)].
In a preferred ~"l~o~i",t,"~, the coating has a durometer hardness between about 70A and 75D.
o 218~628 Preferably, the ooating is between 20 to 30 mils thick and may comprise a pigment.
In another aspect, the invention also provides a hockey stick c~",~,isi"g a blade ooated in ac.,u,.ldl,-,e with the teachings of the present invention.
As embodied and broadly described herein, the invention also provides a prooess for ooating a hockey stick blade, the process comprising the step of applying to a blade a coating cu",,u,i:,;"3 polyurethane and having a durometer hardness of at least 7ûA, the prooess being carried out in the absenoeof or subsldl ,li~:'y in the absence of solvent.
In a preferred ~Illbodi~ , the prooess oomprises the steps of:
a) reacting a mixture of toluene-2,4-diisocyanate and toluene-2,6-diisocyanate with an a,(l)-glycol having between 2 and 6 carbon aloms, mixtures thereof or a low molecular weight polymer thereof to form a urethane prepolymer;
b) mixing a diamine with an a,o~-glyool havin3 between 2 and 6 carbon atoms or mixtures thereof to provide an amine c~" ~,u0~1~1 ,L, c) mixin3 the urethane prepolymer and the amine c~" ~,uol)el ,L to form a coatin3 uulll,uo~iLil)~l, and 2~80628 d) applying the cul "~osiliù" to the blade.
In a preferred ~" l~dil "e"l, the urethane prepolymer and the amine component are heated to a L~ e of about 70~C i 1~C before being admixed and applied to the blade.
Most preferably, the urethane prepolymer of step a) is made by reacting a mixture of toluenQ-2,4-diisocyanate and toluene-2,6-diisocyanate withan a-hydro~-hydroxypoly (oxy-1 ,4-butanediyl) and the amine cc l l ,pol1e~ ll of step b) is a mixture of 4,4'-methylene dianiline with an a-hydro-t~)-hydroxypoly [oxy(methyl-1,2 I,:I,anediyl)]. Preferably, the process is canried out in the absence of or suu~ldl lli~lly in the absence of solvent.
The blade coated in acculddllGe with the invention has the advantage of preventing a~eltndlt:d wear due to harsher playing surfaces while reducing friction. The inventor has also discovered that the coating of the present invention is advantageous when used on traditional ice hockey rinks.
Indeed, although ice surfaces are not as harsh as roller hockey surfaces, ice hockey stick blades are l1u~ eless subjected to abrasion. This condition should be avoided since as a result of the abrasion, water tends to penetrate inside the blade and reach the fibreglass, if any, thereby contributing to the cleld" ,i, l~liol~ of the cu" ,,uu"~"t~ of the stick which, over time, induces structural ~ ~180628 failure to the stick. This problem may be avoided by providing an ice hockey stick blade with the coating of the present invention.
Other objects and features of the invention will become apparent by reference to the following desu, i,uLiol~ of a preferred ~" Ibodi, "e"~.
DESCfi,. I ION OF A PREI LI~REu EMBODIMENT
The inventors have discovered that the objects of the present invention could be achieved by providing a coating having a durometer har~ness of at least about 70A when measured in accu, ~Ito ,~e with the ASTM D-2240 test.More precisely, the inventors have realized that a suitable coating having such properties may be obtained by using a cu" I,uOailiul ~ .u" lu(iail ,9 polyurethane or a mixture of polyurethane and polyurea.
In acc~"~ance with a preferred ~ uodi~ L of the invention, a coating is provided on the lower edge of the blade of a hockey stick. For the purpose of this , ~ ' ,, the e~, ~s~iu" "lower edgeD is intended to cover the portion of the blade that is in contact with a surface of play. The coating can be applied on the entire edge or simply on the area that contacts the surface of play such as, for example, the heel portion. Similarly, the blade could be pro\/ided ~ ~18~28 with a coating that is thicker at the heel portion and thinner at the front portion.
In yet another ~",I,o.li",e"~, the coating could be applied on the entire blade.
A coating according to a hrst ~ o.li~ l of the invention may consist of a polyurethane made by reacting an isocyanate and a polyol.
The isocyanate may be a diisocyanate or a triisocyanate. Suitable diisocyanates for use in preparing the coating of the present invention comprisepreferably a mixture of toluene-2,4-diisocyanate and toluene-2,6-diisocyanate and their derivatives. A preferred diisocyanate is an d~J~lU,~lllldl~ly ~0:20 mixture of toluene-2,4-diisocyanate and toluene-2,6-diisocyanate. Such a mixture is cu"""t~ available and is sold under the trademark MONDUR TD-80 (Product of Bayer). Other suitable diisocyanate include diphenylmethane diisocyanate, naphthylene diisocyanate, a,(,l-alkylene diisocyanates such as he,xd",t:l~,ylene diisocyanate and its derivatives an homologues. Suitable triisocyanates include triphenylmethane-pp'p" triyl triisocyanate.
Suitable polyhydroxy compounds (polyols) that react with the diisocyanates or triisocyanates include diols or triols. Amongst the suitable diols are a,l,~-glycols having between 2 and 6 carbon atoms or mixtures thereoF, the glycols being preferably straight chain. A most preferred diol is a-hydro-~
hydroxypoly (oxy-1 ,4-butanediyl) having a molecular weight of about 1000 or a g ~ 2180628 molecular weight of about 2000 or blends thereof. Such products are co"""e,N~ 'y available under the L,dd~",arks TERATHANE 1000 and 2000 (products of DuPont). The use of triols is also COIll~lllr 3~. Amongst the suitable triols are polyoxypropylene triols. However the use of triols may make it more difficult to control the properties of the coating u u" ~o~ iu~.
The coating of the pr~3sent invention may also comprise some of the additives that are commonly found in such c~" ,~.osilions. Amongst the additivesare pigments used to add colour to the coating. These pigments may be carbon black titanium dioxide or iron oxide and are usually added in an amount not ~xceedi"g 1%. The cu",uosiliu" may also comprise a slip agent cu",~.dli~le therewith to provide good slip properties to the coating. Examples of slip agents include fat~y acids derivatives such as oleamide. When present these agents are added in an amount not exceeding 0.1%. To prevent ~llu~u;ll~lllicdl dey, d~dliUI I and acc~31e, dled oxidation of the coating as a result of exposure to UV radiation there may also be provided a UV stabilizer. Both the choic~3 and the type of UV stabilizer may be d~ '~ lllill~d by the person skilled in the art.
Other additives such as hllers dl lliO~iddl IL~ 1 ,iche,le, ~ or emulsifiers may also be included in the cc " ,~,osilion.
The coating should be within the specified range since a coating having a durometer hardness below about 70A may be too soft and may not allow the player to benefit from the reduced friction. On the other hand the inventor has realized that a coating having a durometer hardness above about 75D may have a tendency to become brittle and as a result the durometer hardness of the coating should not exceed 75D. However the person skilled in the art will realize that the maximum value for the hardness may only depend on the desired: ,~ and this limitation should not be i"~, u, ~ in a llmiting manner.
The person skilled in the art will realize that it is possible to adjust the hardness of the coating by using various additives or by modifying the type of isocyanate or polyol so that the durometer hardness will fall within the scope of the present invention. Such Illo.liri.dliu~s may be d~ ~ .",i"ed by rcutine testing.
A coating according to a second e",L,o~i",e"L of the present invention comprises a mixture of polyurethane and polyurea and is made from mixing a urethane prepolymer with an amine c~" ,u~n~"~. It may also comprise further additives such as the ones previously " ,e, lliul ,ed.
The urethane prepolymer is prepared by reacting an isocyanate with a polyol as described in relation with the first ~",L)odi",e"L. The hydroxy~roupsofth=p It Iwillthusr=adwith~h= socy=ntt~egloupsot~hedilswanat=
218~628 to form a urethane prepolymer. However, unlike the first e",L,o~i",e"~ in vvhichthe coating comprises only polyurethane and additives, if any, the molar ratio of the polyol to the isocyanate is d~ " ,i"ed so that the urethane prepolymer will have isocyanate terminal groups, hence the use of the e,~y, ~:,SiO,l "prepolymer".
Preferably, the ratio of polyol to isocyanate is chosen so that there will be between 6% to 10% excess diisocyanate in the urethane prepolymer.
The isocyanate terminal groups of the urethane prepolymer are then mixed with an amine c~"~,uollel ,~ to form a coating co",,u~silion cu,"p, isi"g a mixture of polyurethane and polyurea.
The amine ~",,uu"~"~ is preferably a diamine. Suitable diarnines include a,~,~-alkyl~, n~ idl l lil ,e having preferably between 2 to 6 carbon atoms and aromatic diamines such as 4,4'-methylene bis(2-.,1,1u,ud, " ,e), 2,4-toluene diamine,diethyl or 4,4'-methylene dianiline.
While it is possible to mix the urethane prepolymer directly with the amine c~" ,,,~one"~, it is however preferable, for handling purposes, if the amine ~u,",uu"e"~ is mixed with a suitable glycol that acts as a chain extender. Thus,the amine cu,,,,uon~ may be a diamine mixed with an a,~-glycol having between 2 and 6 carbon atoms or mixtures thereof. Most preferably, the mixture is obtained by mixing equal amounts of 4,4'-methylene dianiline with an ~ ~180~28 app,u~i,,,dLely 75:25 mixture of two o:-hydro-("-hydroxypoly [oxy(methyl-12-e:llldl~ediyls)] having a molecular weight of about 1000 and about 500 respectively.
The person skilled in the art will realize that it may be possible to use other amine ~ ~" IpUI~ or mixtures provided that the a~ui~,l liO" It:LI iC ratio is adjusted to take into cu"~ide,dliol~ the variations in molecular weight.
Examples of other suitable amine Cu~pO~ include 4 4-methylene bis(2-~:1 llul Udl "' ,e) or 2 4-toluene diamine diethyl. Similarly other glycols such as a-hydro-~l)-hydroxypoly (oxy-1 4-butanediyl) could be used.
Additives such as the ones described in relation with the first e,,l~o~i,,,e"I may also be used.
The invention will be further u"~e, ~luod by the desu, i~iu" of the following example that co" ~t~s a preferred e"ILo~i,"e"l of the invention and that should not be construed in a limiting manner:
~ ~18~628 Example 1 COMPOSITION
I~.~,.. 'i~ It %bvweiaht Mixture A (urethane ~ pol~., ) MONDUR TD-80 ' ~30 TERATHANE 1000 and 2000 2 ~60 mixture B (amine ~ .u..- .~t and additives) 4,4'-methylene dianiline ~5 a-hydro-~t-hydroxypoly [oxy(methyl-1 ,2-ethanediyl)] 3 ~5 carbon black ~0.25 t a~ 80:20 mixture of toluene-2,4-diisocyanate and toluene-2~6~;icl~cy-~ ~
2 u~ so:1 o mix~ure of two ~-hydro ~ (oxy-1 ,4-butanediyls) having mol,ecular weights of about 1000 and about 2000, respec~tvely.
3 ~ 75 :25 mixture of two c~-hydro-~)-hydroxypoly loxy(methyl-1 ,2 .~ Itaving molecular weights of about 1000 and about soo, respectively.
The i"y" ~tdittl 1~ of mixture A were mixed to3ether in a first chamber andwereheatedtoatemperatureofabout70~Ci10~C. Similarly, the illyl~tdittllI:~
of mixture B, including any other additives, were mixed together in a second chamber and were also heated to a temperature of about 70~Ci1 0~C.
Mixtures A and B were then mixed together in a 2:1 ratio (two part mixture A and one part mixture B) and the resulting uu" ~,uO~iIiul ~ was applied to a wood hockey stick blade by using a spray gun. A PROBLER gun (Product of Glas-Craft) with a 17:1 fluid to air ratio was found to be suitable for this. The use of such a spray gun facilitates the coating operation since the two mixtures A and B are only mixed at the tip of the gun thereby preventing premature ' i~Iiu,, 2~8~628 of the c~" ,~.o ,it;." ,. In a variant, the tip of the spray gun may be removed and the cul~ " , may be applied as a bead. The person skilled in the art will however realize that the co",,u~a~ n may be applied to the blade using other similar equipment or other coating techniques known in the art. A prefenTed thickness for roller hockey is d,U,UI o,~i" Idl~ly from 10 to 50 mils and preferably from 20 to 30 mils but the thickness may vary according to the intended use. Also, the coatingmay be applied in a single ,, " " , or in a series of d,U~.)Ii~ d~iUl~s In the latter case however, each coating is not left to dry before the other coating is applied.
The c~,, ,,uosiliol~ was then left to dry under normal con.litions and solidified thereby providing an abrasion resistant coating. A period of between 40 to 60 seconds was found to be sufFicient to complete the drying.
PHYSICAL PROPERTIES
The coating of example 1 exhibited the following ~, u~ s.
Property Result Test 20 Hardness (durometerShore D) 50Di5D ' ASTM D-2240 Tensile strength (psi) 3200 ASTM D-412 Elongation (%) 300 ASTM D-412 Resiliency (%) 45 ASTM D-2632 This value is equivalent to a durometer hardness of at least 90A.
~ 2180628 The coating of example 1 was tested on pavement and on an ice rink and provided sdlibrduLury results.
While the coating of the second ~"ILJo.li,"~"L was prepared by a urethane prepolymer with an amine uu, I ,pu~ ,e"~, in yet a third ~" ,~ou'i" ,e"L, the coating could be prepared by mixing a diisocyanate with a mixture cu,,,p, isi, lg a polyol, an amine cu",,uo,~ and additives, if any. For apparent reasons, a less dangerous diisocyanate such as diphenylmethane diisocyanate should preferably be used in such an ~:IllL)odilllt:llt instead toluene-2,4-diisocyanat3 and 1 û toluene-2,6-diisocyanate.
Because of the relatively fast ' ' ~ " 1 time of the cc " I~ObitiOI 1, the use of the coating of the present invention may improve the efficiency of the manufacturing process of hockey stick blade thereby lowering costs.
Furthermore, the use of the coating according to the invention avoid the use of volatile organic compounds which might be released into the dll "~b,ulle, ~ and is thus safer for the environment.
The above desu,i,u~iu,~ of a preferred e",L)odi",~"l should not be 2û i, l~, ,u, ~l~d in any limiting manner since variations and, ~ri"~" ,e, ILb are possible which are within the spirit and scope of the present invention. The scope of theinvention is defined in the appended claims and their equivalents.
Claims (16)
1. A hockey stick blade having a lower edge for contacting a surface of play, at least a portion of said lower edge bearing an abrasion resistant coating comprising polyurethane, said coating having a durometer hardness of at least about 70A.
2. A blade as defined in claim 1 wherein said coating comprises polyurethane and polyurea.
3. A blade as defined in claim 2 wherein said coating is made by mixing a urethane prepolymer having isocyanate terminal groups with an amine component.
4. A blade as defined in claim 3 wherein said urethane prepolymer is made by reacting a mixture of toluene-2,4-diisocyanate and toluene-2, 6-diisocyanate with an .alpha.,.omega.-glycol having between 2 and 6 carbon atoms, mixtures thereof or a low molecular weight polymer thereof and wherein said amine component is a diamine which is mixed with an .alpha.,.omega.-glycol having between 2 and 6 carbon atoms or mixtures thereof.
5. A blade as defined in claim 4 wherein said urethane prepolymer is made by reacting a mixture of toluene-2,4-diisocyanate and toluene-2,
6-diisocyanate with an .alpha.-hydro-.omega.-hydroxypoly (oxy-1,4-butanediyl) and wherein said amine component is a mixture of 4,4'-methylene dianiline with an .alpha.-hydro-.omega.-hydroxypoly[oxy(methyl-1,2-ethanediyl)]..
6. A hockey stick blade having a lower edge for contacting a surface of play, at least a portion of said lower edge bearing an abrasion resistant coating having a durometer hardness of at least about 70A, said coating being made by mixing a urethane prepolymer with an amine component, said urethane prepolymer being made by reacting an approximately 80:20 mixture of toluene-2,4-diisocyanate and toluene-2,6-diisocyanate with an approximately 90:10 mixture of two .alpha.-hydro-.omega.-hydroxypoly (oxy-1,4-butanediyls) having molecular weights of about 1000 and about 2000, respectively, said amine component being a mixture of 4,4'-methylene dianiline with an approximately 75:25 mixture of two .alpha.-hydro-.omega.-hydroxypoly [oxy(methyl-1,2-ethanediyls)] having molecular weights of about 1000 and about 500, respectively.
6. A hockey stick blade having a lower edge for contacting a surface of play, at least a portion of said lower edge bearing an abrasion resistant coating having a durometer hardness of at least about 70A, said coating being made by mixing a urethane prepolymer with an amine component, said urethane prepolymer being made by reacting an approximately 80:20 mixture of toluene-2,4-diisocyanate and toluene-2,6-diisocyanate with an approximately 90:10 mixture of two .alpha.-hydro-.omega.-hydroxypoly (oxy-1,4-butanediyls) having molecular weights of about 1000 and about 2000, respectively, said amine component being a mixture of 4,4'-methylene dianiline with an approximately 75:25 mixture of two .alpha.-hydro-.omega.-hydroxypoly [oxy(methyl-1,2-ethanediyls)] having molecular weights of about 1000 and about 500, respectively.
7. A blade as defined in claim 1 wherein said coating is made by mixing a diisocyanate with an amine mixture comprising an amine component, an .alpha.,.omega.-glycol having between 2 and 6 carbon atoms, mixtures thereof or a low molecular weight polymer thereof.
8. A blade as defined in claim 7 wherein said diisocyanate is diphenylmethane diisocyanate and wherein said amine mixture comprises an .alpha.-hydro-.omega.-hydroxypoly (oxy-1,4-butanediyl), 4,4'-methylene dianiline and an .alpha.-hydro-.omega.-hydroxypoly [oxy(methyl-1,2-ethanediyl)].
9. A blade as defined in claim 1 wherein said coating is between 20 to 30 mils thick.
10. A blade as defined in claims 1, 2, 3, 4, 5, 6, and 7, wherein said coating has a durometer hardness between about 70A and about 75D.
11. A hockey stick comprising a blade coated in accordance with any claim 1.
12. A process for coating a hockey stick blade, said process comprising the step of applying to a blade a coating comprising polyurethane and having a durometer hardness of at least 70A, said process being carried out in the absence of or substantially in the absence of solvent.
13. A process for coating a hockey stick blade, said process comprising the steps of:
a) reacting a mixture of toluene-2,4-diisocyanate and toluene-2, 6-diisocyanate with an .alpha.,.omega.-glycol having between 2 and 6 carbon atoms, mixtures thereof or a low molecular weight polymer thereof to form a urethane prepolymer;
b) mixing a diamine with an .alpha.,.omega.-glycol having between 2 and 6 carbon atoms or mixtures thereof to provide an amine component;
c) mixing said urethane prepolymer and said amine component to form a coating composition; and d) applying said composition to said blade.
a) reacting a mixture of toluene-2,4-diisocyanate and toluene-2, 6-diisocyanate with an .alpha.,.omega.-glycol having between 2 and 6 carbon atoms, mixtures thereof or a low molecular weight polymer thereof to form a urethane prepolymer;
b) mixing a diamine with an .alpha.,.omega.-glycol having between 2 and 6 carbon atoms or mixtures thereof to provide an amine component;
c) mixing said urethane prepolymer and said amine component to form a coating composition; and d) applying said composition to said blade.
14. A process as defined in claim 13 wherein said urethane prepolymer and said amine component are heated to a temperature of about 70°C ~ 10°C
before being admixed and applied to said blade.
before being admixed and applied to said blade.
15. A process as defined in claim 14 wherein the urethane prepolymer of step a) is made by reacting a mixture of toluene-2,4-diisocyanate and toluene-2,6-diisocyanate with an .alpha.-hydro-.omega.-hydroxypoly (oxy-1,4-butanediyl) and wherein the amine component of step b) is a mixture of 4,4'-methylene dianiline with an .alpha.-hydro-.omega.-hydroxypoly [oxy(methyl-1,2-ethanediyl)].
16. A process as defined in claims 13 or 14, said process being carried out in the absence of or substantially in the absence of solvent.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2180628 CA2180628A1 (en) | 1996-07-05 | 1996-07-05 | Hockey stick blade having an abrasion resistant coating and process for coating said blade |
| AU30220/97A AU3022097A (en) | 1996-07-05 | 1997-06-13 | Hockey stick blade having an abrasion resistant coating and process for coating said blade |
| PCT/CA1997/000419 WO1998001189A1 (en) | 1996-07-05 | 1997-06-13 | Hockey stick blade having an abrasion resistant coating and process for coating said blade |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2180628 CA2180628A1 (en) | 1996-07-05 | 1996-07-05 | Hockey stick blade having an abrasion resistant coating and process for coating said blade |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2180628A1 true CA2180628A1 (en) | 1998-01-06 |
Family
ID=4158553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2180628 Abandoned CA2180628A1 (en) | 1996-07-05 | 1996-07-05 | Hockey stick blade having an abrasion resistant coating and process for coating said blade |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU3022097A (en) |
| CA (1) | CA2180628A1 (en) |
| WO (1) | WO1998001189A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008083502A1 (en) * | 2007-01-12 | 2008-07-17 | Garth Wells | Hockey stick blade sleeve |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2330083C (en) | 2000-01-07 | 2010-04-13 | Jas. D. Easton, Inc. | Hockey stick |
| US7963868B2 (en) | 2000-09-15 | 2011-06-21 | Easton Sports, Inc. | Hockey stick |
| CA2357331C (en) | 2000-09-15 | 2010-07-20 | Jas D. Easton, Inc. | Hockey stick |
| US7232386B2 (en) | 2003-05-15 | 2007-06-19 | Easton Sports, Inc. | Hockey stick |
| US7914403B2 (en) | 2008-08-06 | 2011-03-29 | Easton Sports, Inc. | Hockey stick |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2487208A1 (en) * | 1980-07-07 | 1982-01-29 | Boniface Jacques | Hockey stick with head covered by a durable plastic - pref. polypropylene sheathed with polyurethane and moulded in situ |
| US4404353A (en) * | 1981-08-20 | 1983-09-13 | Dataproducts Corporation | Urethane elastomer for printing belts and process therefor |
| US4556703A (en) * | 1984-05-14 | 1985-12-03 | American Cyanamid Company | Low heat buildup polyurethane compositions and articles |
| US4786703A (en) * | 1987-04-15 | 1988-11-22 | Air Products And Chemicals, Inc. | Process for the preparation of polyisocyanate prepolymers and polyurethanes having high temperature performance and low hysteresis |
| US5332212A (en) * | 1993-01-22 | 1994-07-26 | Dsb Industries, Inc. | Coated hockey stick blade |
| WO1996002385A1 (en) * | 1994-07-15 | 1996-02-01 | H.B. Fuller Licensing & Financing, Inc. | Non-skid water based coating |
-
1996
- 1996-07-05 CA CA 2180628 patent/CA2180628A1/en not_active Abandoned
-
1997
- 1997-06-13 AU AU30220/97A patent/AU3022097A/en not_active Abandoned
- 1997-06-13 WO PCT/CA1997/000419 patent/WO1998001189A1/en active Application Filing
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008083502A1 (en) * | 2007-01-12 | 2008-07-17 | Garth Wells | Hockey stick blade sleeve |
Also Published As
| Publication number | Publication date |
|---|---|
| AU3022097A (en) | 1998-02-02 |
| WO1998001189A1 (en) | 1998-01-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |