CA2086109A1 - Coating composition and method - Google Patents
Coating composition and methodInfo
- Publication number
- CA2086109A1 CA2086109A1 CA002086109A CA2086109A CA2086109A1 CA 2086109 A1 CA2086109 A1 CA 2086109A1 CA 002086109 A CA002086109 A CA 002086109A CA 2086109 A CA2086109 A CA 2086109A CA 2086109 A1 CA2086109 A1 CA 2086109A1
- Authority
- CA
- Canada
- Prior art keywords
- isocyanate
- equivalent weight
- coating
- golf ball
- acrylic polymer
- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
-
- 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
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
-
- 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
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
-
- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
-
- 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
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
- C08G18/8029—Masked aromatic polyisocyanates
-
- 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
- A63B2102/32—Golf
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
Improved coatings particularly useful for golf balls are based on modified acrylic urethanes. The coatings have high film clarity, gloss, durability, flexibility and resistance to weathering and abrasion. The coating composition is applied, typically by spraying and preferably after application of a suitable primer. The coating composition is a mixture of a hard acrylic polymer having a functionality reactive with an isocyanate and isocyanate-reactive modifiers, reacted together in a solvent with an isocyanate such as polyisocyanate. Golf balls with these coatings exhibit improved hardness and flexibility.
Description
W092/19656 PCr/US92/03402 f~ 20~G109 COATING COMPOSITION AND METHOD
D~CRI2TION
~elated ~.s. A~licatio~ Dat~
This is a continuation-in-part o~ co-pending U.S. ap-plication Ser. No. 07/691,552, filed April 25, 1991.
~;
Tech~ical ~ield The invention relates to improved coatings, more particularly to coatings especially useful ~or golf balls due to their superior properties uniquely adapted for this useO
Golf balls must be durable and have an attractive appearance throughout their lives, which are now extended due to the high durability of new materials of construction.
The advent of cut resistant golf balls, particularly those having covers made of ~igh impact natural or synthetic polymexic materials such a~ those ionomer resins sold under the trademark Surlyn0, has increased the need for durable coatings to improve the appearance of the balls. Conven-tionally, these balls are provided with a primer coat, e.g. an organic-solvent based epoxy or a water-based polymer, and are then over coated with a polyurethane which provides desirable proper~ies in terms of flexibility, but achieves some desir-able properties only at the expense of others.
There is a present need for an improved coating com position which is capable of providing high film clarity, ., ,. ,,, ~ .. ;,, ,,, .... ;. .. ~
: : , , ..................... ;, . ... .. . .
, : ' ., , . . : ; :~ :
~;
: WO92J19656 PCT/US92/0~02 -2- c 2a~l0s gloss, durability, flexibility and resistance to weathering and abrasion.
:. . ;
~isclo~ure of Inve~tion It is an object of the invention to provide a coating composition especially adapted for uses which require impact durability and flexibility.
It is another object of the invention to provide a coating composition which provides high clarity and hish gloss and also has good resistance to weathering and abrasion.
It is a more specific object of the invention to pro-vide a coating composition having all of the above properties for sporting goods, such as golf balls.
These and other objects are achieved by the pres~nt invention which provides an improved coating composition, an improved coating method, and improved coatings and articles employing ~hem.
The coating composition of the invention comprises: (a) a hard acrylic polymer having a functionality reactive with an isocyanate; (b) an isocyanate; (c) a solvent for application flow and leveling t and (d) a modifying re~in which is also isocyanate reactive but imparts flexibility and/or abrasion resistance to the final coating. In preferred embodiments, the acxylic polymer, the isocyanate, and the isocyanate-reac-tive modifiere each have equivalent weights of at least about 200.
The method of the invention comprises: (a) optionally applying a primer layer to a substrate, such as natural or s, ~ ... ..... . , .. , . . :: . ..
WO92/19656 PCT/US92/0~02 !~ -3- 2 ~ 9 synthetic polymer resins such as ionomeric pol~mers; (b) spraying onto the surface a coating composition as defined above, and .(c) drying and curing the coating.
The coated article comprises: a substrate, such as a golf ball having a primed ionomeric layer overcoated with a dried, cured layer of an acrylic urethane coating.
Be~t Mo~e For Carrvi~g Out the In~e~tio~
The invention will be described below in greater detail with specific rPference to the use of golf ball coatings.
Other uses, e.g. bowling pins, are intended, but are not detailed for the sake of conciseness.
The invention, in one of its preferred aspects, pro-vides a modified acrylic urethane coating system for Surlyn~
covered golf balls. The coating system comprises an acrylic resin having a functionality reactive with a polyisocyanate.
The functionality can be a member selected from the group consisting of hydroxyl, amine, amide, carboxyl and mixtures of any of these. The acrylic typically has a functional group (e.g., hydroxyl) equivalent weight on a solïd resin basis of from 200 to 2000, preferably from 500 to 700t The modifiers function similarly to pla~ticizer6 and/or ~urface hardeners but are reactive with the isocyanate. The polyisocyanate can be a suitable prepolymer, homopolymer or copolymer of diiso-cyanates such as toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI). The products, e.g. ionomer-golf balls, will exhibit good hardness, flexibility, weather resistance, brightness, abrasion resis-tance and clarity.
Good golf ball cover materials have a balance of forming and final properties including good flowability, good .~ , . "
W092/19656 P~T/U~92/0~02 ~ Q9 -4-mold release, moderate sti~ness, high abrasion resistance, high tear strength, high resilience, and the like. Preferred polymeric materials are ionomer resins comprising copolymers of ethylene and unsaturated monocarboxylic acids which are available under the trademark Surlyn~ from ~.I. DuPont de Nemours Company of Wilmington, Delaware. These ionic copoly-mers are sodium, lithium, or zinc salts of reaction products of olefins having from 2 to 8 carbon atoms and unsaturated monocarboxylic acids having from 3 to 8 carbon atoms. The carboxylic acid groups of the copolymer may be totally or partially neutralized.
The use of a single ionic copolymer as golf ball cover stock is described in U.5. Patent No. 3,454,280 issued July 8, 1969. The use of mixed Surlyn0 resins is described in U.S.
Patent No. 3,819,768 issued June 25, 1974. Other ionic co-polymers are described in U.S. Patent No. 3,264,272 issued August 2, 1966.
In addition to the above-described preferr~d Surlyn~
resins, other thermoplastic materials and thermosetting materials including natural and syn~hetic polymeric materials can be employed. Balata and gutta percha, previously avail~
able as natural materials are now available as synthetic polymeric materials and are suitable for use. in accordance with this invention. Other materials include urethane as well as other synthetic polymers. The golf ball comprises a highly resilient core ha~ing a cover stock of one of these high im-pact materials, or mixtures thereof.
To prepare the elastomeric, e.g. ionomer, or other substrate for coating with the composition of this invention, a primer effective to promote bonding between the coating and the substrate is preferably employed. Among the effective primers are solvent-based or water-based epoxies and water-based acrylic or urethane polymers. Exemplary of the .. . . . .......................... . . . ... .
. . : - :; :: .. :~ :
wos2/ls6s6 PCT/US92/0~02 ~; ! .
~ ~8~109 epoxy primers is a two component solvent-based epoxy, avail-able as TCL-3707/3631 from Technical Coatings Laboratory, Inc, Avon, Connecticut. Exemplary of the water-based primers is a modified acrylic polymer coating available as TCL-5500 from the same source as above. Other primers, available from other suppliers are also effective. Primers are not always requlred, but do enhance results for most users.
The primer is applied according to specifications for the particular material, e.g. spraying to a thickness of about 1/8 to 1/2 mil. Epoxy primers of the type identified above are typically cured for from 10 minutes to 24 hours, at ~rom room temperature to 150F. The epoxy coating has to be essen tially solvent free before top coating. The water-based poly-mers are typically cured for from 1 to 45 minutes at from room temperat~re to 150F.
Following priming, the coating compo6ition o~ the invention is applied. The coating composition itself com-prises an acrylic resin having an isocyanate reactive func-tionality, an isocyanate, a solvent, and a isocyanate-reactive modifier. It can also have, as desired, various catalysts, pramoters, driers, hardeners, brighteners and the like.
The acrylic resin can be a homo or copolymer of acrylic monomers having the isocyanate-reactive functionalities, e.g.
selected from the group consisting o~ hydroxyl, amine, amide, carboxyl, and mixtures of any of these. One embodiment employs predominantly hydroxyl group isocyanate reactive functionalities. The monomers can be any of those effective for pxoducing the desired acrylic resins, and can, for example, be selected from the group consisting of acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, acryloni-', ' ' ' ' , '. ' , , ~ , ~ ' . ~ . ' ~ 6- r trile, acrylamide, and the like monomers and mixtures of these. Prefsrred blends compxise any of the above and the like, and preferred embodiments are hard polymers having a minimum of 10% styrene in the monomer composition. Some embodiments have at least about 20% styrene. Some coatings of this invention contain acrylic polymers having less than about 1% of alphabeta ethylenically unsaturated carboxylic acid monomers.
The acrylic reæinC will be prepared in conventional fashion to have isocyanate-functional equivalent weights typically above 200 and below ~000. T~pically this involves solution vinyl poly~erization where the monomers are added to a catalyst-containing sol~ent gradually over the course of the reaction and in amounts effective to give the desired ~ui-valent weight. Preferred eguivalent weights will be in the range of from 400 to about 600 on a resin solid basis. One preferr~d acrylic resin is based on methyl ~ethacrylate and hydroxypropyl methacrylate monomers and has an equivalent weight of between 500 and 600, on a solids ~asis. Typical available resins of ~his type are Rohm and Haas's AU 608, AT-400, AT-410 and Henkel'~ G-Cure 867 and 868. It is pre-ferable to mix the reactive isocyanate in a two component system just prior to application. A blend of solvents is employed to achieve a suitable solids concentration and viscosity for good mixing, application and reaction. One material of this type is TCL-5823, available from Technical Coatings Laboratory, Inc.
The isocyanate component of the coating system can be any suitable isocyanate, includiny prepolymers, homopolymers or copolymers of diisocyanates such as toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diiso cyanate (IPDI), and the like. The various families of iso-cyanates that have been investigated have been hexamethylene diisocyanate biuret, hexamethylene/toluene diisocyanate .
, ': , ~: :. ,. : ~, . : .
wosz~1s6s6 PCT/US92/0~02 -7-208~109 copolymers, toluene diisocyante bicyanurate trimer, toluene diisocyante/trimethyol propane adduct, isophorone diisocyanate (IPDI) based prepolymer toluene diisocyanate multi-functional prepolymer, and hexamethylene diisocyanate trimer.
The isocyanates are prepared in known manner and typically have equivalent weights to the hydroxyl or other acrylic isocyanate reactive group of at least about 100, and preferably from 200 to 800, e.g. 300 to 500 on a solids basis. The isocyanate6 are prefQrably employed as prepolymer solutions with suitable solids, concentrations and viscosities for effective mixing application, drying and curing.
A one package polyurethane system may al~o be used.
This system uses a blocked isocyanate such as Miles's Des-modur~ BL-1185. Limitations of use may be related to the thermo-plastic characteristics of the substrate.
The modifiers are typically added to the final reaction mixture as a preblend with the acrylic resin. The modifiers employed in the coating composition will be those which are effective to impart flexibility and abrasion resistance to the final coating. Organic plasticizers can also be used in this acrylic coating composition. Monomeric and pol~meric plastici-zers allow the coating to increase its workability and its flexibility. Phthalic anhydride esters such as dioctyl phtha-late, dibutyl phthalate and dicyclohexyl phthalate may be used. Epoxidized soya oils, oil free and oil modified alkyds can also be incorporated. Alkylene glycol esters of benzoic and adipate acid such as ethylene glycol adipate benzoate, neopentyl adipate benzoate and ethylene glycol adipate ben-zoate phthalhte can also be used in the coating compostion.
The preferred modifier is sufficiently reactive to prevent migration to the surface of the coating. The modifiers preferably have isocyanate reactive functional groups at an ., .
: : . . : : :. . :. ~ :, :
... " ' . ~:: . , ., ..,~.. ;
. :: : :: , . :: .. .
.
WO92/19656 PCT/US9Z/0~02 q~ .9 -8-equivalent weight ef~ective for this purpose, e.g. under lO,000 and preferably from 200 to 2000 on a solids basis.
Among the suitable modifiers are the members selected from the group consisting of cellulosic esters; silicones;
silanes; caprolactones; vinyl polymers; acrylic polymers with carboxyl, amino or hydroxyl functionality such as Henkel's G-Cure~ 105P70 and G-CureX 806; polyesters; polyester-modified, hydroxylfunctional polydimethylsiloxane; and mixtures of these. Preferred among these are caprolactones, such as Tone~ polyols, available from Union Carbide Cor-poration, Danbury, Connecticut and characterized by a hydroxyl equivalent weight of about lO00. Some more specific examples of suitable modifiers include the following: caprolactone polyols di and tri~unctional, with equivalent weights 200 to 1800, preferably 800 to 1200; polyesters having equivalent weights of 300 to 1500; cellulosic modifiers including cellulose acetate butyrate or cellulo~e acetate proprionate;
and solution vinyls, including the medium to low viscosity types.
The solvents employed for the acrylic and the iso-cyanat~ components will be chosen ~or their primary role as well as their co~patibility with the overall composition, the mixing of the various components, the compatibility ~ith the intended substrate and the ease of application, drying and curing of the coating composition. Among the solvents are n-butyl acetate, xylene, toluene, propylene, glycol monomethyl ether acetate, ethyl acetate, CellosolveZ acetate, and the like. All solvents are essentially water-free, i.e., urethane grade.
Isocyanates are the crosslinkers used in the acrylic urethane coating. These are polymeric in nature, when mixed stoichiometrically with the acrylic urethane polyol produces a tough flexible coating. The mix ratio for the polyol-iso-,.. , :,: ., ,.. .,: :
WO92/196s~ PCT/US92~q~2 ~ ! .
~9~~ 0 ~ ~1 0 9 .
cyanate combination are measured as the amount of NCO iso~cyanate needed to react with an equivalent amount ~f hydroxyl groups. Stoichiometrically the amount of NCO/OH ratio needed would be 1.0/1.0; however excess isocyanate is generally used since the isocyanate is moisture sensitive and its effective~
ness would diminish upon exposure to air. The range of NC0~0 can be from 1.0/1 up to 1.8/1. Changing the mix ratios wi~l effect the physical properties of the coating: hardness~ dur~
ability and pot li~e are very common variables when this ratio is changed. The preferred range for the NCO/O~ is about lol/l to 1.5/1.
In addition to the above, the coating composition can include other additives in amounts effective for their in-tended purposes. For example, catalysts such as dibutyltin dilaurate, metal driers, or tertiary am~nes can be employed a~
effective levels, e.g., of O.O1 to 0.05~ based on vehicle solids. The type and level may bç adjusted as ~eeded to achieve desired pot life and cure time~. Also, ~arious coLor additives such as titanium dioxide, driers guch as cobalt salts, managanese salts or calcium salts, and op~ical brigh~-eners and ultraviolet absorbers such a~ Ciba-Geigy Uvitex O~, Tinuvin~ 328 and Tinuvin~ 770, or equivalents, can be employed in amounts desired.
The coating composition is formed for application by blending an acrylic resin solution and an isocyanate solution prior to application. The proportions of isocyanate and acrylic resins will be as noted above. The acrylic resin premix will typically contain: from 50% to 100%, e.g. from 60 to 98% acrylic resin solids, up to 50% modifier solids; e.gO 2 to 40%; and from 20 to 90% solvent based on the weight of the solids. Similarly, an isocyanate premix is formed containing from 20 to 80, preferably from 68 to 72% isocyanate solids and from 20 to 80, preferably from 32 to 38%. These amounts can be varied widely as processing needs and capabilities dictate.
, .. . .. :~
W092/19656 PCT/US92/0~2 ~' 9 -lo-cl,9~
Various spray techniques can be used to apply these coatings. These include, but are not necessarily limited to, air atomized with pressure or suction feed with or without heat, airles~, airless hot ~pray and electrostatic. For the purposes of this invention, a Binks No. 18 suction spray gun equipped with a 62 fluid nozzle, a 62 fluid cap and a 66 PG
air cap can very effectively be used. The application tech~
nique should ensure a uniform coating on the ball or other substitutes. In a production application, two to four fixed guns may be required to give a uniform coating. The coating is applied in any desired thickness, typically to give a final thickness of from 1/2 to 1 mil.
The applied urethane coating will cur~ as typical urethanes. ~he rate of cure will depend upon temperature and humidity. The preferred curing cycle is 24 hours at 105~F and 50% relative hu~idity. Faster cures can be achieved by in~
creasing the cure temperature. For example, the balls can cure in 2 hours at 140F and 50% relativ~ humidity. Various catalysts or cakalyst combinations ~an be used to help a~
celerate the cure.
The following example~ are presented to further illus-trate and explain the invention and are not to be taken as limiting in any respect. Unless otherwise indicated, all parts and percentages are based on the weight of the parti-cular composition or component at the indicated stage of processing.
~nDle ~` This example describes the preparation of a coating composition according to the invention, and the application of that composition to a Surlyn~ ionomer covered gol~ ball to produce an improved golf ball o~ the invention. An acrylic ~ premix is prepared by blending an acrylic resin prepared from ;:
WO92/19656 PCT/VS92~Q.~02 11- 208~109 2~hydroxyethyl acrylate, having a hydroxyl equivalent weight of 600 (solids basis), with the following other components in the indicated amountsO
Acrylic Resin Premix Com~onent Parts Acrylic resin (solids) 36.5 Caprolactone 2.5 VAGD~ vinyl solution (20% solids) 12.0 (ethyl acetate solvent, from Union Carbide) Cellulosic solution t20% solids) 2.5 ~cellulose acetate butyrate polymer in ethyl acetate ~, solvent) Solvents 46~4 (ethyl acetate and ; toluene, 1:1) -~ Miscellaneous additives 0.1 (catalyst and optical ; brightener) 100. 0 Separately, an isocyanate premix is prepared from a hexamethylene diisocyanate biuret prepolymer having an equivalent weight of about 190, based on solids, by mixing the following components in the amounts indicated.
IsocYanate Premix Component Parts Isocyanate prepolymer (solids) 30 Solvents (Xylene and n-butyl acetate) 70 :. : , ,............ , .... . ., :. .:... ... ..
- . ., : : ..
W092/19656 PCT/US92/~02 ,A sprayable coating composition is then prepared by mixing 100 parts o~ the acrYlic resin premix with 51 parts by weight of the isocyanate premix~
A Surlyn~ ionomer covered golf ball is prepared for coating with the above coating composition by first priming the surface by spray coating with a solution of a commercial solvent-based epoxy primer (TCL-3707/3631~ to provide a primer coating thickness of 1/8 to 1/4 mil. The primer coating is dried for 45 minutes at 145F.
The sprayable coating composition is then applied by spraying by means o~ a Binks no. 18 suction spray yun equipped with a 62 fluid nozzle, a 62 fluid cap, and a 66 PG air capO
The coating is sufficient to provide a ~ilm thickness of l/2 to 3/4 mil. The coatin~ is flashed at 75~F ~or 20 minutes and then cured for 24 hours at 145F.
~Mpl~ 2 The procedure of Example 1 is repeated but this time the premixes and their proportions meet the following cri-`: teria:
Acrylic Resin Premix ComPOnent Parts Acrylic resin (solids) 18.0 Solvent 44.5 Polyester 6.0 Vinyl solution ~20% solids) 2B.3 Cellulosic solution (20% solids) 2.5 Miscellaneous additives 0.7 100. 0 , . , : . ,. ,, , . ..... ;:
' ~ ' ' i `: ' , , -. ''~''.'; :.
:
W092/19656 PC~ gX~ 2 -13- 2~861 ~9 Isocvanate Premix component Parts Isocyanate prepolymer 310 6%
(HDI/HDI - TDI copolymer/
TDI-trimethyolpropane) Solvents 68~4%
(n-butyl acetate, xylene) 1~0. 0 The ratio of acrylic resin premix to isocyanate premix for preparing a coating composition is 100:37.5.
. .
~ le 3 The procedure for Example 2 iB again repeated but this time the premix isocyanate and the proportions of the two premixes are modified as follows:
: Isocyanate Premix ComPonent Parts Isocyanate (solids) 31.6 (~DI biuret/H.DI-TDI copolymer/
TDI Bicyanurate copolymer) Solvent 68.4 100.O
~ he ratio of acrylic resin premix to isocyanate premix for preparing a composition was 100038. To these~ two components are added 73.0 parts of a blended thinner com ~ prising aromatic hydrocarbons and esters. Flash conditions : are modified to account for the high level of solvent in the . coating composition.
',:
::
WO 92/19656 PCI/lUS92tO36~102 ~, A, ~
~!~ 'r --14 ~
~amDle Acrvlic Resin Premix Com~onent . Parts Acrylic resin solution (60~ solids) 36.5 Caprolactone 7.5 Vinyl solution (20% solids) 10.1 Solvent 45.0 Miscellaneous additives0.9 100. 0 ~socyanate Premix Component Parts Isocyanate prepolymer (solids) 32.0 :~ (50-50 HDI/TDI-HDI) : Solvent ~8.0 (ethyl acetate, butyl acatate, toluene) 100.O
The two premixes are mixed at a ratio of acrylic resin premix to isocyanate premix o~ 100:36.5.
.~-~a~ampl~ s The procedure of Example 1 is again ~epeated ~ut : this time the premix isocyanate and the proportions of the two : premixes are modified as follows:
.
Acrylic Resin Premix Component Parts Acrylic r~esin (solids) 30.0 Vinyl solution (20~ solids) 10.8 ~: Solvent 57.3 : Miscellaneous additives 1.9 100.0 WO92/19656 PCT/US9~/034~2 -15- 2 0 8 6l 09 Isocvanate Premix - Component Parts Isocyanate (solids) 42.0 (TDI prepolymer) Solvent 5~.0 100. 0 .
; The ratio of acrylic resin premix to isocyanate premix for preparing a composition was lO0:36.5.
' B~amPlQ-6 The procedure of Example 5 is again repeated but this time the premix i~ocyanate is modified as follows-Isocvanate Premix Component Parts Isocyanate (solids) 59.8 (IPDI prepolymer) Solvent 40.2 100. 0 The two premix solutions are mixed at a ratio ofacrylic resin solution to isocyanate solution of 100:36.5.
E~ampls 7 The procedure of Example l is again repeated but ; this time the isocyanate premix and the proportions of the two premixes are modified as follows:
~; :
:~' .. , ,; .. , .,,. , ..... " : ; :;, ::,. :, . . . .. :
; , ,,: ~ :- ' ' i'' ' : ':""''`''' :' : ' ' ' " ' :
WO92/19656 PCT/~S~ 2 ~ 16-Acrylic Resin Premix Component Parts Acrylic (solids) 21.9 Caprolactone (solids) 1.6 Vinyl solution (20% ~olids) 12.0 Solvent 63.2 Silicone (solids) lo O
Miscellaneous additives0.3 100. 0 Isocyanate Premix Component Parts IsocyanatP (solids) 46.0 (HDI/TDI-HDI copolymer) Solvent 54.0 lOOo O
~.
The ratio of acrylic resin premix to isocyanate premix for preparing a composition was 100:40.3.
B~amE~e 8 The procedure for Example 1 is again repeated but ` this time the premix isocyanate and the proportions of the two premixes are modified as follows:
Acrylic Resin Premix ; Com~onent ?arts Acrylic (solids) 36.5 Caprolactone (solids) 7.5 Vinyl solution (20% solids) 10.0 Solvent 45.1 Miscellaneous additives o.g 100.0 , : , ., :, ,. . . :
r ' - '.,' ', '., : , ' ,. i: . , , l ! ' W092/19656 PCT/US92/0~02 ~ 17 2086109 _socyanate Premix ~ Com~onent Parts : Isocyanate (solids) `~ HDI prepolymer 1804 TDI prepolymer 27.6 Solvent 540 '.
' lOOo ~) i The ratio of acrylic resin premix to isocyanate premix for preparing a composition was 100:38.2.
.
:
mpl0 9 The procedure for Example 8 is again repeated but this time the premix isocyanate and the proportions of the two premixes are modified as follows:
Isocyanate Premix Component Parts Isocyanate (solids) HDI prepolymer 1308 TDI prepolymer 32.2 Solvent 54 100.O
The rakio of acrylic resin premix to isocyanate premix for preparing a composition was 100:40.
Bsa~le_lO
~ The procedure for Example 8 is again repeated but .: this time the premix isocyanate and the proportions of the two premixes are modified as follows:
. " ~
' :,''~
: .
.' r WO92/19656 PCT/US92/0.~02 ~6~ 18-Isocyanate Premix Component~ Parts Isocyanate (solids) HDI prepolymer 11.5 TDI prepolymer 34.5 Solvent 54.0 100. 0 The ratio of acrylic resin premix to isocyanate - premix for preparing a composition was 100:41.
: .
The above description is for the purpose of teaching the person of ordinary skill in the art how to practice the present invention, and it is not intended to detail all of those obvious modifications and variations of it which will become apparent to the skilled worker upon reading the description. It is intended, however, that all such obvious modifications and variations be included within the scope of the invention which is defined by the following claimsO
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D~CRI2TION
~elated ~.s. A~licatio~ Dat~
This is a continuation-in-part o~ co-pending U.S. ap-plication Ser. No. 07/691,552, filed April 25, 1991.
~;
Tech~ical ~ield The invention relates to improved coatings, more particularly to coatings especially useful ~or golf balls due to their superior properties uniquely adapted for this useO
Golf balls must be durable and have an attractive appearance throughout their lives, which are now extended due to the high durability of new materials of construction.
The advent of cut resistant golf balls, particularly those having covers made of ~igh impact natural or synthetic polymexic materials such a~ those ionomer resins sold under the trademark Surlyn0, has increased the need for durable coatings to improve the appearance of the balls. Conven-tionally, these balls are provided with a primer coat, e.g. an organic-solvent based epoxy or a water-based polymer, and are then over coated with a polyurethane which provides desirable proper~ies in terms of flexibility, but achieves some desir-able properties only at the expense of others.
There is a present need for an improved coating com position which is capable of providing high film clarity, ., ,. ,,, ~ .. ;,, ,,, .... ;. .. ~
: : , , ..................... ;, . ... .. . .
, : ' ., , . . : ; :~ :
~;
: WO92J19656 PCT/US92/0~02 -2- c 2a~l0s gloss, durability, flexibility and resistance to weathering and abrasion.
:. . ;
~isclo~ure of Inve~tion It is an object of the invention to provide a coating composition especially adapted for uses which require impact durability and flexibility.
It is another object of the invention to provide a coating composition which provides high clarity and hish gloss and also has good resistance to weathering and abrasion.
It is a more specific object of the invention to pro-vide a coating composition having all of the above properties for sporting goods, such as golf balls.
These and other objects are achieved by the pres~nt invention which provides an improved coating composition, an improved coating method, and improved coatings and articles employing ~hem.
The coating composition of the invention comprises: (a) a hard acrylic polymer having a functionality reactive with an isocyanate; (b) an isocyanate; (c) a solvent for application flow and leveling t and (d) a modifying re~in which is also isocyanate reactive but imparts flexibility and/or abrasion resistance to the final coating. In preferred embodiments, the acxylic polymer, the isocyanate, and the isocyanate-reac-tive modifiere each have equivalent weights of at least about 200.
The method of the invention comprises: (a) optionally applying a primer layer to a substrate, such as natural or s, ~ ... ..... . , .. , . . :: . ..
WO92/19656 PCT/US92/0~02 !~ -3- 2 ~ 9 synthetic polymer resins such as ionomeric pol~mers; (b) spraying onto the surface a coating composition as defined above, and .(c) drying and curing the coating.
The coated article comprises: a substrate, such as a golf ball having a primed ionomeric layer overcoated with a dried, cured layer of an acrylic urethane coating.
Be~t Mo~e For Carrvi~g Out the In~e~tio~
The invention will be described below in greater detail with specific rPference to the use of golf ball coatings.
Other uses, e.g. bowling pins, are intended, but are not detailed for the sake of conciseness.
The invention, in one of its preferred aspects, pro-vides a modified acrylic urethane coating system for Surlyn~
covered golf balls. The coating system comprises an acrylic resin having a functionality reactive with a polyisocyanate.
The functionality can be a member selected from the group consisting of hydroxyl, amine, amide, carboxyl and mixtures of any of these. The acrylic typically has a functional group (e.g., hydroxyl) equivalent weight on a solïd resin basis of from 200 to 2000, preferably from 500 to 700t The modifiers function similarly to pla~ticizer6 and/or ~urface hardeners but are reactive with the isocyanate. The polyisocyanate can be a suitable prepolymer, homopolymer or copolymer of diiso-cyanates such as toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI). The products, e.g. ionomer-golf balls, will exhibit good hardness, flexibility, weather resistance, brightness, abrasion resis-tance and clarity.
Good golf ball cover materials have a balance of forming and final properties including good flowability, good .~ , . "
W092/19656 P~T/U~92/0~02 ~ Q9 -4-mold release, moderate sti~ness, high abrasion resistance, high tear strength, high resilience, and the like. Preferred polymeric materials are ionomer resins comprising copolymers of ethylene and unsaturated monocarboxylic acids which are available under the trademark Surlyn~ from ~.I. DuPont de Nemours Company of Wilmington, Delaware. These ionic copoly-mers are sodium, lithium, or zinc salts of reaction products of olefins having from 2 to 8 carbon atoms and unsaturated monocarboxylic acids having from 3 to 8 carbon atoms. The carboxylic acid groups of the copolymer may be totally or partially neutralized.
The use of a single ionic copolymer as golf ball cover stock is described in U.5. Patent No. 3,454,280 issued July 8, 1969. The use of mixed Surlyn0 resins is described in U.S.
Patent No. 3,819,768 issued June 25, 1974. Other ionic co-polymers are described in U.S. Patent No. 3,264,272 issued August 2, 1966.
In addition to the above-described preferr~d Surlyn~
resins, other thermoplastic materials and thermosetting materials including natural and syn~hetic polymeric materials can be employed. Balata and gutta percha, previously avail~
able as natural materials are now available as synthetic polymeric materials and are suitable for use. in accordance with this invention. Other materials include urethane as well as other synthetic polymers. The golf ball comprises a highly resilient core ha~ing a cover stock of one of these high im-pact materials, or mixtures thereof.
To prepare the elastomeric, e.g. ionomer, or other substrate for coating with the composition of this invention, a primer effective to promote bonding between the coating and the substrate is preferably employed. Among the effective primers are solvent-based or water-based epoxies and water-based acrylic or urethane polymers. Exemplary of the .. . . . .......................... . . . ... .
. . : - :; :: .. :~ :
wos2/ls6s6 PCT/US92/0~02 ~; ! .
~ ~8~109 epoxy primers is a two component solvent-based epoxy, avail-able as TCL-3707/3631 from Technical Coatings Laboratory, Inc, Avon, Connecticut. Exemplary of the water-based primers is a modified acrylic polymer coating available as TCL-5500 from the same source as above. Other primers, available from other suppliers are also effective. Primers are not always requlred, but do enhance results for most users.
The primer is applied according to specifications for the particular material, e.g. spraying to a thickness of about 1/8 to 1/2 mil. Epoxy primers of the type identified above are typically cured for from 10 minutes to 24 hours, at ~rom room temperature to 150F. The epoxy coating has to be essen tially solvent free before top coating. The water-based poly-mers are typically cured for from 1 to 45 minutes at from room temperat~re to 150F.
Following priming, the coating compo6ition o~ the invention is applied. The coating composition itself com-prises an acrylic resin having an isocyanate reactive func-tionality, an isocyanate, a solvent, and a isocyanate-reactive modifier. It can also have, as desired, various catalysts, pramoters, driers, hardeners, brighteners and the like.
The acrylic resin can be a homo or copolymer of acrylic monomers having the isocyanate-reactive functionalities, e.g.
selected from the group consisting o~ hydroxyl, amine, amide, carboxyl, and mixtures of any of these. One embodiment employs predominantly hydroxyl group isocyanate reactive functionalities. The monomers can be any of those effective for pxoducing the desired acrylic resins, and can, for example, be selected from the group consisting of acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, acryloni-', ' ' ' ' , '. ' , , ~ , ~ ' . ~ . ' ~ 6- r trile, acrylamide, and the like monomers and mixtures of these. Prefsrred blends compxise any of the above and the like, and preferred embodiments are hard polymers having a minimum of 10% styrene in the monomer composition. Some embodiments have at least about 20% styrene. Some coatings of this invention contain acrylic polymers having less than about 1% of alphabeta ethylenically unsaturated carboxylic acid monomers.
The acrylic reæinC will be prepared in conventional fashion to have isocyanate-functional equivalent weights typically above 200 and below ~000. T~pically this involves solution vinyl poly~erization where the monomers are added to a catalyst-containing sol~ent gradually over the course of the reaction and in amounts effective to give the desired ~ui-valent weight. Preferred eguivalent weights will be in the range of from 400 to about 600 on a resin solid basis. One preferr~d acrylic resin is based on methyl ~ethacrylate and hydroxypropyl methacrylate monomers and has an equivalent weight of between 500 and 600, on a solids ~asis. Typical available resins of ~his type are Rohm and Haas's AU 608, AT-400, AT-410 and Henkel'~ G-Cure 867 and 868. It is pre-ferable to mix the reactive isocyanate in a two component system just prior to application. A blend of solvents is employed to achieve a suitable solids concentration and viscosity for good mixing, application and reaction. One material of this type is TCL-5823, available from Technical Coatings Laboratory, Inc.
The isocyanate component of the coating system can be any suitable isocyanate, includiny prepolymers, homopolymers or copolymers of diisocyanates such as toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diiso cyanate (IPDI), and the like. The various families of iso-cyanates that have been investigated have been hexamethylene diisocyanate biuret, hexamethylene/toluene diisocyanate .
, ': , ~: :. ,. : ~, . : .
wosz~1s6s6 PCT/US92/0~02 -7-208~109 copolymers, toluene diisocyante bicyanurate trimer, toluene diisocyante/trimethyol propane adduct, isophorone diisocyanate (IPDI) based prepolymer toluene diisocyanate multi-functional prepolymer, and hexamethylene diisocyanate trimer.
The isocyanates are prepared in known manner and typically have equivalent weights to the hydroxyl or other acrylic isocyanate reactive group of at least about 100, and preferably from 200 to 800, e.g. 300 to 500 on a solids basis. The isocyanate6 are prefQrably employed as prepolymer solutions with suitable solids, concentrations and viscosities for effective mixing application, drying and curing.
A one package polyurethane system may al~o be used.
This system uses a blocked isocyanate such as Miles's Des-modur~ BL-1185. Limitations of use may be related to the thermo-plastic characteristics of the substrate.
The modifiers are typically added to the final reaction mixture as a preblend with the acrylic resin. The modifiers employed in the coating composition will be those which are effective to impart flexibility and abrasion resistance to the final coating. Organic plasticizers can also be used in this acrylic coating composition. Monomeric and pol~meric plastici-zers allow the coating to increase its workability and its flexibility. Phthalic anhydride esters such as dioctyl phtha-late, dibutyl phthalate and dicyclohexyl phthalate may be used. Epoxidized soya oils, oil free and oil modified alkyds can also be incorporated. Alkylene glycol esters of benzoic and adipate acid such as ethylene glycol adipate benzoate, neopentyl adipate benzoate and ethylene glycol adipate ben-zoate phthalhte can also be used in the coating compostion.
The preferred modifier is sufficiently reactive to prevent migration to the surface of the coating. The modifiers preferably have isocyanate reactive functional groups at an ., .
: : . . : : :. . :. ~ :, :
... " ' . ~:: . , ., ..,~.. ;
. :: : :: , . :: .. .
.
WO92/19656 PCT/US9Z/0~02 q~ .9 -8-equivalent weight ef~ective for this purpose, e.g. under lO,000 and preferably from 200 to 2000 on a solids basis.
Among the suitable modifiers are the members selected from the group consisting of cellulosic esters; silicones;
silanes; caprolactones; vinyl polymers; acrylic polymers with carboxyl, amino or hydroxyl functionality such as Henkel's G-Cure~ 105P70 and G-CureX 806; polyesters; polyester-modified, hydroxylfunctional polydimethylsiloxane; and mixtures of these. Preferred among these are caprolactones, such as Tone~ polyols, available from Union Carbide Cor-poration, Danbury, Connecticut and characterized by a hydroxyl equivalent weight of about lO00. Some more specific examples of suitable modifiers include the following: caprolactone polyols di and tri~unctional, with equivalent weights 200 to 1800, preferably 800 to 1200; polyesters having equivalent weights of 300 to 1500; cellulosic modifiers including cellulose acetate butyrate or cellulo~e acetate proprionate;
and solution vinyls, including the medium to low viscosity types.
The solvents employed for the acrylic and the iso-cyanat~ components will be chosen ~or their primary role as well as their co~patibility with the overall composition, the mixing of the various components, the compatibility ~ith the intended substrate and the ease of application, drying and curing of the coating composition. Among the solvents are n-butyl acetate, xylene, toluene, propylene, glycol monomethyl ether acetate, ethyl acetate, CellosolveZ acetate, and the like. All solvents are essentially water-free, i.e., urethane grade.
Isocyanates are the crosslinkers used in the acrylic urethane coating. These are polymeric in nature, when mixed stoichiometrically with the acrylic urethane polyol produces a tough flexible coating. The mix ratio for the polyol-iso-,.. , :,: ., ,.. .,: :
WO92/196s~ PCT/US92~q~2 ~ ! .
~9~~ 0 ~ ~1 0 9 .
cyanate combination are measured as the amount of NCO iso~cyanate needed to react with an equivalent amount ~f hydroxyl groups. Stoichiometrically the amount of NCO/OH ratio needed would be 1.0/1.0; however excess isocyanate is generally used since the isocyanate is moisture sensitive and its effective~
ness would diminish upon exposure to air. The range of NC0~0 can be from 1.0/1 up to 1.8/1. Changing the mix ratios wi~l effect the physical properties of the coating: hardness~ dur~
ability and pot li~e are very common variables when this ratio is changed. The preferred range for the NCO/O~ is about lol/l to 1.5/1.
In addition to the above, the coating composition can include other additives in amounts effective for their in-tended purposes. For example, catalysts such as dibutyltin dilaurate, metal driers, or tertiary am~nes can be employed a~
effective levels, e.g., of O.O1 to 0.05~ based on vehicle solids. The type and level may bç adjusted as ~eeded to achieve desired pot life and cure time~. Also, ~arious coLor additives such as titanium dioxide, driers guch as cobalt salts, managanese salts or calcium salts, and op~ical brigh~-eners and ultraviolet absorbers such a~ Ciba-Geigy Uvitex O~, Tinuvin~ 328 and Tinuvin~ 770, or equivalents, can be employed in amounts desired.
The coating composition is formed for application by blending an acrylic resin solution and an isocyanate solution prior to application. The proportions of isocyanate and acrylic resins will be as noted above. The acrylic resin premix will typically contain: from 50% to 100%, e.g. from 60 to 98% acrylic resin solids, up to 50% modifier solids; e.gO 2 to 40%; and from 20 to 90% solvent based on the weight of the solids. Similarly, an isocyanate premix is formed containing from 20 to 80, preferably from 68 to 72% isocyanate solids and from 20 to 80, preferably from 32 to 38%. These amounts can be varied widely as processing needs and capabilities dictate.
, .. . .. :~
W092/19656 PCT/US92/0~2 ~' 9 -lo-cl,9~
Various spray techniques can be used to apply these coatings. These include, but are not necessarily limited to, air atomized with pressure or suction feed with or without heat, airles~, airless hot ~pray and electrostatic. For the purposes of this invention, a Binks No. 18 suction spray gun equipped with a 62 fluid nozzle, a 62 fluid cap and a 66 PG
air cap can very effectively be used. The application tech~
nique should ensure a uniform coating on the ball or other substitutes. In a production application, two to four fixed guns may be required to give a uniform coating. The coating is applied in any desired thickness, typically to give a final thickness of from 1/2 to 1 mil.
The applied urethane coating will cur~ as typical urethanes. ~he rate of cure will depend upon temperature and humidity. The preferred curing cycle is 24 hours at 105~F and 50% relative hu~idity. Faster cures can be achieved by in~
creasing the cure temperature. For example, the balls can cure in 2 hours at 140F and 50% relativ~ humidity. Various catalysts or cakalyst combinations ~an be used to help a~
celerate the cure.
The following example~ are presented to further illus-trate and explain the invention and are not to be taken as limiting in any respect. Unless otherwise indicated, all parts and percentages are based on the weight of the parti-cular composition or component at the indicated stage of processing.
~nDle ~` This example describes the preparation of a coating composition according to the invention, and the application of that composition to a Surlyn~ ionomer covered gol~ ball to produce an improved golf ball o~ the invention. An acrylic ~ premix is prepared by blending an acrylic resin prepared from ;:
WO92/19656 PCT/VS92~Q.~02 11- 208~109 2~hydroxyethyl acrylate, having a hydroxyl equivalent weight of 600 (solids basis), with the following other components in the indicated amountsO
Acrylic Resin Premix Com~onent Parts Acrylic resin (solids) 36.5 Caprolactone 2.5 VAGD~ vinyl solution (20% solids) 12.0 (ethyl acetate solvent, from Union Carbide) Cellulosic solution t20% solids) 2.5 ~cellulose acetate butyrate polymer in ethyl acetate ~, solvent) Solvents 46~4 (ethyl acetate and ; toluene, 1:1) -~ Miscellaneous additives 0.1 (catalyst and optical ; brightener) 100. 0 Separately, an isocyanate premix is prepared from a hexamethylene diisocyanate biuret prepolymer having an equivalent weight of about 190, based on solids, by mixing the following components in the amounts indicated.
IsocYanate Premix Component Parts Isocyanate prepolymer (solids) 30 Solvents (Xylene and n-butyl acetate) 70 :. : , ,............ , .... . ., :. .:... ... ..
- . ., : : ..
W092/19656 PCT/US92/~02 ,A sprayable coating composition is then prepared by mixing 100 parts o~ the acrYlic resin premix with 51 parts by weight of the isocyanate premix~
A Surlyn~ ionomer covered golf ball is prepared for coating with the above coating composition by first priming the surface by spray coating with a solution of a commercial solvent-based epoxy primer (TCL-3707/3631~ to provide a primer coating thickness of 1/8 to 1/4 mil. The primer coating is dried for 45 minutes at 145F.
The sprayable coating composition is then applied by spraying by means o~ a Binks no. 18 suction spray yun equipped with a 62 fluid nozzle, a 62 fluid cap, and a 66 PG air capO
The coating is sufficient to provide a ~ilm thickness of l/2 to 3/4 mil. The coatin~ is flashed at 75~F ~or 20 minutes and then cured for 24 hours at 145F.
~Mpl~ 2 The procedure of Example 1 is repeated but this time the premixes and their proportions meet the following cri-`: teria:
Acrylic Resin Premix ComPOnent Parts Acrylic resin (solids) 18.0 Solvent 44.5 Polyester 6.0 Vinyl solution ~20% solids) 2B.3 Cellulosic solution (20% solids) 2.5 Miscellaneous additives 0.7 100. 0 , . , : . ,. ,, , . ..... ;:
' ~ ' ' i `: ' , , -. ''~''.'; :.
:
W092/19656 PC~ gX~ 2 -13- 2~861 ~9 Isocvanate Premix component Parts Isocyanate prepolymer 310 6%
(HDI/HDI - TDI copolymer/
TDI-trimethyolpropane) Solvents 68~4%
(n-butyl acetate, xylene) 1~0. 0 The ratio of acrylic resin premix to isocyanate premix for preparing a coating composition is 100:37.5.
. .
~ le 3 The procedure for Example 2 iB again repeated but this time the premix isocyanate and the proportions of the two premixes are modified as follows:
: Isocyanate Premix ComPonent Parts Isocyanate (solids) 31.6 (~DI biuret/H.DI-TDI copolymer/
TDI Bicyanurate copolymer) Solvent 68.4 100.O
~ he ratio of acrylic resin premix to isocyanate premix for preparing a composition was 100038. To these~ two components are added 73.0 parts of a blended thinner com ~ prising aromatic hydrocarbons and esters. Flash conditions : are modified to account for the high level of solvent in the . coating composition.
',:
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WO 92/19656 PCI/lUS92tO36~102 ~, A, ~
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~amDle Acrvlic Resin Premix Com~onent . Parts Acrylic resin solution (60~ solids) 36.5 Caprolactone 7.5 Vinyl solution (20% solids) 10.1 Solvent 45.0 Miscellaneous additives0.9 100. 0 ~socyanate Premix Component Parts Isocyanate prepolymer (solids) 32.0 :~ (50-50 HDI/TDI-HDI) : Solvent ~8.0 (ethyl acetate, butyl acatate, toluene) 100.O
The two premixes are mixed at a ratio of acrylic resin premix to isocyanate premix o~ 100:36.5.
.~-~a~ampl~ s The procedure of Example 1 is again ~epeated ~ut : this time the premix isocyanate and the proportions of the two : premixes are modified as follows:
.
Acrylic Resin Premix Component Parts Acrylic r~esin (solids) 30.0 Vinyl solution (20~ solids) 10.8 ~: Solvent 57.3 : Miscellaneous additives 1.9 100.0 WO92/19656 PCT/US9~/034~2 -15- 2 0 8 6l 09 Isocvanate Premix - Component Parts Isocyanate (solids) 42.0 (TDI prepolymer) Solvent 5~.0 100. 0 .
; The ratio of acrylic resin premix to isocyanate premix for preparing a composition was lO0:36.5.
' B~amPlQ-6 The procedure of Example 5 is again repeated but this time the premix i~ocyanate is modified as follows-Isocvanate Premix Component Parts Isocyanate (solids) 59.8 (IPDI prepolymer) Solvent 40.2 100. 0 The two premix solutions are mixed at a ratio ofacrylic resin solution to isocyanate solution of 100:36.5.
E~ampls 7 The procedure of Example l is again repeated but ; this time the isocyanate premix and the proportions of the two premixes are modified as follows:
~; :
:~' .. , ,; .. , .,,. , ..... " : ; :;, ::,. :, . . . .. :
; , ,,: ~ :- ' ' i'' ' : ':""''`''' :' : ' ' ' " ' :
WO92/19656 PCT/~S~ 2 ~ 16-Acrylic Resin Premix Component Parts Acrylic (solids) 21.9 Caprolactone (solids) 1.6 Vinyl solution (20% ~olids) 12.0 Solvent 63.2 Silicone (solids) lo O
Miscellaneous additives0.3 100. 0 Isocyanate Premix Component Parts IsocyanatP (solids) 46.0 (HDI/TDI-HDI copolymer) Solvent 54.0 lOOo O
~.
The ratio of acrylic resin premix to isocyanate premix for preparing a composition was 100:40.3.
B~amE~e 8 The procedure for Example 1 is again repeated but ` this time the premix isocyanate and the proportions of the two premixes are modified as follows:
Acrylic Resin Premix ; Com~onent ?arts Acrylic (solids) 36.5 Caprolactone (solids) 7.5 Vinyl solution (20% solids) 10.0 Solvent 45.1 Miscellaneous additives o.g 100.0 , : , ., :, ,. . . :
r ' - '.,' ', '., : , ' ,. i: . , , l ! ' W092/19656 PCT/US92/0~02 ~ 17 2086109 _socyanate Premix ~ Com~onent Parts : Isocyanate (solids) `~ HDI prepolymer 1804 TDI prepolymer 27.6 Solvent 540 '.
' lOOo ~) i The ratio of acrylic resin premix to isocyanate premix for preparing a composition was 100:38.2.
.
:
mpl0 9 The procedure for Example 8 is again repeated but this time the premix isocyanate and the proportions of the two premixes are modified as follows:
Isocyanate Premix Component Parts Isocyanate (solids) HDI prepolymer 1308 TDI prepolymer 32.2 Solvent 54 100.O
The rakio of acrylic resin premix to isocyanate premix for preparing a composition was 100:40.
Bsa~le_lO
~ The procedure for Example 8 is again repeated but .: this time the premix isocyanate and the proportions of the two premixes are modified as follows:
. " ~
' :,''~
: .
.' r WO92/19656 PCT/US92/0.~02 ~6~ 18-Isocyanate Premix Component~ Parts Isocyanate (solids) HDI prepolymer 11.5 TDI prepolymer 34.5 Solvent 54.0 100. 0 The ratio of acrylic resin premix to isocyanate - premix for preparing a composition was 100:41.
: .
The above description is for the purpose of teaching the person of ordinary skill in the art how to practice the present invention, and it is not intended to detail all of those obvious modifications and variations of it which will become apparent to the skilled worker upon reading the description. It is intended, however, that all such obvious modifications and variations be included within the scope of the invention which is defined by the following claimsO
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Claims (20)
1. A coating composition comprising (a) a hard acrylic polymer having a functionality reactive with an isocyanate and an equivalent weight of at least about 200;
(b) an isocyanate having an equivalent weight of at least about 200;
(c) an isocyanate-reactive modifier having an equivalent weight of at least about 200 effective to improve flexibility while retaining good abrasion resistance; and (d) a solvent.
(b) an isocyanate having an equivalent weight of at least about 200;
(c) an isocyanate-reactive modifier having an equivalent weight of at least about 200 effective to improve flexibility while retaining good abrasion resistance; and (d) a solvent.
2. A composition according to claim 1 wherein the acrylic polymer has an equivalent weight of between about 200 and about 2000, the isocyanate has an equivalent weight of between about 200 and about 2000, and the isocyanate-reactive modifier has an equivalent weight of between about 200 and about 2000.
3. A composition according to claim 2 wherein the acrylic polymer has an equivalent weight of between about 500 and about 700, the isocyanate has an equivalent weight of between about 300 and about 500, and the isocyanate-reactive modifier has an equivalent weight of between about 300 and about 1500.
4. A composition according to any of claims 1 to 3 wherein the acrylic polymer comprises monomers selected from the group consisting of styrene, methyl methacrylate, hydroxypropyl meth-acrylate monomers, and mixtures of these, and has a styrene content of at least about 10%.
5. A composition according to any of claims 1 to 4 wherein the functionality reactive with an isocyanate in the acrylic polymer is selected from the group consisting of hydroxyl, carboxyl, amine, amide, and mixtures of these, the isocyanate is a polyisocyanate comprising a prepolymer, homopolymer, copolymer or biuret comprising residues of at least one of toluene diisocyanate, hexamethylene diisocyanate, and iso-phorone diisocyanate, and the isocyanate-reactive modifier is selected from the group consisting of cellulosic esters, silicones, silanes, caprolactones, vinyl polymers, acrylic polymers, polyesters, and polyester-modified hydroxy func-tional polydimethylsiloxanes.
6. A composition according to any of claims 1 to 5 wherein the functionality reactive with isocyanate on the acrylic polymer is an hydroxyl group, and the ratio of the isocyanate equivalent weight to the hydroxyl equivalent weight in the coating varies between about 1 to 1 to about 1.5 to 1.
7. A composition according to any of claims 1 to 6 wherein the acrylic polymer contains less than about 1% of an alpha-beta ethylenically unsaturated carboxylic acid monomer.
8. A method for enhacing the surface characteristics of a substrate comprising applying to the surface of the substrate a coating composition as set forth in any of claims 1 to 7, and drying and curing the coating composition.
9. A method far enhancing the surface characteristics of a substrate comprising first mixing the acrylic polymer, the isocyanate-reactive modifier, and the solvent of any of claims 1 to 7, and then adding the isocyanate of any of claims 1 to 7 before applying the composition to the surface of the sub-strate.
10. A method according to claims 8 or 9 wherein the substrate is a golf ball having a cover stock of ionomeric material.
11. A golf ball made according to the method of claim 10.
12. A method according to claim 10 wherein a primer is applied to the ionomeric golf ball cover stock prior to applying the coating composition.
13. A golf ball comprising (a) a highly resilient core having a cover stock of high impact material; and (b) a coating on said cover stock comprising an acrylic polymer having a functionality reactive with an iso-cyanate and an equivalent weight of at least about 200; an isocyanate having an equivalent weight of at least about 200;
an isocyanate-reactive modifier having an equivalent weight of at least about 200 effective to improve flexibility while retaining good abrasion resistance; and a solvent.
an isocyanate-reactive modifier having an equivalent weight of at least about 200 effective to improve flexibility while retaining good abrasion resistance; and a solvent.
14. A golf ball according to claim 13 further comprising a primer layer between said cover stock and said coating.
15. A golf ball according to claim 14 wherein the primer is selected from the group consisting of epoxies and water-based acrylic or urethane polymers.
16. A golf ball according to any of claims 13 to 15 wherein said cover stock comprises a material selected from the group consisting of ionomer, balata or urethane.
17. A golf ball according to any of claims 13 to 16 wherein the coating is from 0.1 to 1.0 mil in thickness.
18. A golf ball according to any of claims 13 to 17 wherein the isocyanate-reactive modifier is selected from the group consisting of cellulosic esters, silicones, silanes, capro-lactones, vinyl polymers, acrylic polymers, polyesters, and polyester-modified hydroxy functional polydimethylsiloxanes.
19. A golf ball according to any of claims 13 to 18 wherein the isocyanate is a polyisocyanate and the functionality reac-tive with the isocyanate is an hydroxyl group.
20. A golf ball comprising (a) a highly resilient core having a cover stock selected from the group consising of ionomer, balata, urethane and mixtures of these;
(b) a primer layer on said cover stock; and (c) a 0.1 to 1.0 mil thick cross-linked coating on said primer layer, wherein said coating is made by reacting, in a solvent, an equivalent weight of about 500 to about 700.
of an acrylic polymer having a hydroxyl group functionality reactive with an isocyanate, an equivalent weight of about 300 to about 500 of a polyisocyanate, and an equivalent weight of about 300 to about 1500 of an isocyanate-reactive modifier effective to improve flexibility while retaining good abrasion resistance.
(b) a primer layer on said cover stock; and (c) a 0.1 to 1.0 mil thick cross-linked coating on said primer layer, wherein said coating is made by reacting, in a solvent, an equivalent weight of about 500 to about 700.
of an acrylic polymer having a hydroxyl group functionality reactive with an isocyanate, an equivalent weight of about 300 to about 500 of a polyisocyanate, and an equivalent weight of about 300 to about 1500 of an isocyanate-reactive modifier effective to improve flexibility while retaining good abrasion resistance.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US69155291A | 1991-04-25 | 1991-04-25 | |
| US07/691,552 | 1991-04-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2086109A1 true CA2086109A1 (en) | 1992-10-26 |
Family
ID=24776991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002086109A Abandoned CA2086109A1 (en) | 1991-04-25 | 1992-04-24 | Coating composition and method |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA2086109A1 (en) |
| WO (1) | WO1992019656A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998028048A1 (en) | 1996-12-24 | 1998-07-02 | Bridgestone Sports Co., Ltd. | Process for producing golf ball |
| US6005045A (en) * | 1998-02-24 | 1999-12-21 | Ppg Industries Ohio, Inc. | Waterborne, ambient temperature curable film-forming compositions |
| US6103787A (en) * | 1998-03-03 | 2000-08-15 | Acushnet Company | Golf ball cover compositions |
| US6458462B1 (en) | 2000-12-13 | 2002-10-01 | 3M Innovative Properties Company | Sporting goods having a ceramer coating |
| US6596837B2 (en) | 2001-03-27 | 2003-07-22 | Acushnet Company | Abrasion resistant coated golf equipment |
| US7572508B2 (en) | 2004-07-12 | 2009-08-11 | Acushnet Company | Polyurea coatings for golf equipment |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL288151A (en) * | 1961-08-31 | 1900-01-01 | ||
| GB1087566A (en) * | 1965-02-10 | 1967-10-18 | Dunlop Rubber Co | Improvements in and relating to golf balls |
| US3689310A (en) * | 1970-12-21 | 1972-09-05 | Ford Motor Co | Polyester and acrylic rubber-urethane-acrylate paint and painting process |
| US3819768A (en) * | 1972-02-11 | 1974-06-25 | Questor Corp | Golf ball cover compositions comprising a mixture of ionomer resins |
| US3841895A (en) * | 1972-12-29 | 1974-10-15 | Du Pont | Flexible hydrocarbon rubber substrate finished with a thermosetting acrylic enamel |
| US3979540A (en) * | 1975-12-22 | 1976-09-07 | E. I. Du Pont De Nemours And Company | Ionomer resin substrates coated with an epoxy primer and finished with an acrylic coating |
| US4384103A (en) * | 1981-12-28 | 1983-05-17 | Ford Motor Company | High solids urethane coatings I |
| US4379906A (en) * | 1981-12-28 | 1983-04-12 | Ford Motor Company | High solids urethane coatings prepared from a polylisocyanate _ and a polyhydroxy oligmer |
| US4376187A (en) * | 1981-12-28 | 1983-03-08 | Ford Motor Company | High solids urethane coatings with enhanced flexibility and impact strength |
| US4452930A (en) * | 1983-02-10 | 1984-06-05 | Ppg Industries, Inc. | Curable compositions containing novel urethane curing agents |
| US4452963A (en) * | 1983-02-10 | 1984-06-05 | Ppg Industries, Inc. | Low temperature urethane curing agents |
| US4524183A (en) * | 1983-10-31 | 1985-06-18 | Union Carbide Corporation | High solids acrylic coating systems |
| US4656237A (en) * | 1983-10-31 | 1987-04-07 | Union Carbide Corporation | High solids acrylic coating systems |
| NZ214999A (en) * | 1985-02-06 | 1988-09-29 | Albright & Wilson Australia | Polyurethane coating composition |
| US4727099A (en) * | 1986-08-15 | 1988-02-23 | E. I. Du Pont De Nemours And Company | Coating composition containing a reactive urethane component, a hydroxyl containing acrylic polymer having pendent ester groups and a metallic alkylate catalyst |
| US4814382A (en) * | 1986-10-07 | 1989-03-21 | Union Carbide Corporation | Solvent borne high solids coating compositions |
| US5098956A (en) * | 1988-01-22 | 1992-03-24 | S.C. Johnson & Son, Inc. | Polyol blends of low TG and high TG acrylic copolymers |
| US5098952A (en) * | 1988-01-22 | 1992-03-24 | S. C. Johnson & Son, Inc. | Polyol blends of low Tg and high Tg acrylic copolymers |
-
1992
- 1992-04-24 CA CA002086109A patent/CA2086109A1/en not_active Abandoned
- 1992-04-24 WO PCT/US1992/003402 patent/WO1992019656A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO1992019656A1 (en) | 1992-11-12 |
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