CA1200161A - Method for applying abrasion resistant thin polyurethane coatings - Google Patents
Method for applying abrasion resistant thin polyurethane coatingsInfo
- Publication number
- CA1200161A CA1200161A CA000429930A CA429930A CA1200161A CA 1200161 A CA1200161 A CA 1200161A CA 000429930 A CA000429930 A CA 000429930A CA 429930 A CA429930 A CA 429930A CA 1200161 A CA1200161 A CA 1200161A
- Authority
- CA
- Canada
- Prior art keywords
- triisocyanate
- prepolymer
- polyol
- diisocyanate
- solvent
- 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.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/1077—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing polyurethane
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
Abstract
Abstract of the Disclosure A method for applying a thin abrasion resistant polyurethane coating while minimizing exposure to volatile free isocyanate is disclosed.
The method involves forming a hydroxy-terminated prepolymer which is sub-sequently crosslinked using a relatively non-volatile triisocyanate, and applying the material by flow coating or dip coating techniques, rather than spraying, in order to minimize volatilization.
The method involves forming a hydroxy-terminated prepolymer which is sub-sequently crosslinked using a relatively non-volatile triisocyanate, and applying the material by flow coating or dip coating techniques, rather than spraying, in order to minimize volatilization.
Description
3~
METHOD FOR APPLYING
ABRASION RESISTANT THIN POLYURETHANE COATINGS
Background of the Invention Field of the Invention The present invention relates generally to abrasion resistant polyurethane coatings, and more particularly to a method for applying thin polyurethane coatings.
Discussion of the Technology U.S. Patent No. 4,079,160 to Phillipson teaches an optical ele-ment, such as an eyeglass lens, formed of a typical rigid polymeric sub-strate of relatively low scratch resistance coated on at least one surface with a relatively soft, resil;ent and tough, transparent polymeric material.
Spinning techniques are disclosed to be particularly suitable for applying the coating to the lens.
U.S. Patent No. 4,174,240 to Muller teaches laminates wherein gla:3s or glass~like plastics are coated with a transparent film 0.1 to 5 millimeters thick formed from a polyurethane polyurea containing 1 to 20 percent by weight urea groups and 0.001 to 10 percent by weight lateral -COOH groups. The polyurethane polyurea films are formed by solution casting or extrusion and are subsequently laminated to the substrates by the application of heat and pressure.
Summary of the Invention The present invention involves the use of relatively soft, resilient, crosslinked polyurethanes as abrasion resistant coatings. The ~2t~
polyurethanes of the present invention are prepared from aliphatic diiso-cyanates, straight chain polycarbonate diols, and crosslinking agents such as triisocyanates. The crosslinked aliphatic polycarbonate urethane coat-ings of the present invention are applied from solutions of prepolymer and crosslinking agent which are for example flow or dip coated onto a substrate, dri,ed, and cured to preferably form a coating less than 0.005 inch (0.13 millimeter) thick, more preferably about 0.001 to 0.002 inch (0.025 to 0.05 millimeter) thick~ By using a prepolymer and a relatively nonvolatile crosslinking agent, the method of the present invention minimi7es exposure to volatile free isocyanate. Volatilization of isocyanate is Eurther minimized by employing a coatLng technique whereby the substrate to be coated ls contacted with the coating solution in a continuous liquid phase, such as in ~low or dip coating, rather than a spray. The polyurethane coatings of tlle present invention are especialLy useful in aircraft transparencies as abrasion resistant coatings, either on rigid plastic layers such as polycarbonate or acrylic, or on resilient plastic layers such as impact resistant polyurethane in a glass bilayer lamina~e~
Description of the Preferred I~Aml)o(llments _ _ _ _ _ .
~n abrasion resistant, crosslinked aliphatic polyurethane is prepared from a reaction mixture of an aliphatic organic diisocyanate, a polyol, and a high molecular weight triisocyanate. The polyol is preEerably a polycarbonate diol having a molecular weight below 500.
Tetrabutyl titanate catalyst is also preferred in accordance with ~.S.
Patent No. 4,160,853.
The diisocyanate is preferably a cycloaliphatic diisocyanate such as 4,4'~methylene-bis-(cyclohexyl isocyanate). Polyurethanes prepared from _ ~ _ al;phat:Lc lsocyall.ltes, pnrtlcularLy cyc~o<~ atic d-iisocycllla~es, I~.lve good physical and optical properties over a wide temperat-lre range, ancl are not adversely affected by ultraviolet light. In addition to the most prefer-red diisocyanate, 4~4'methylene-bis-(cyclohexyl isocyanate), other suitable aliphatic diisocyanates include 1,4-cyclohexyl diisocyanate, 4,4-isopropyli,dene-bis-(cy~lohexyl isocyanate), and other dinuclear cyclo-alipha~ic diisocyanates, preferably isophorone diisocyanate. Branched diisocyanates such as trimethylhexamethylene diisocyanate may also be used, preferably in combination with 4,4'-methylene-bis-(cyclohexyl isocyanate) or isophorone diisocyanate.
Polyols useful according to the present invention may be licluicl at room temperature or soluble in the reaction mixture. Preferred polyols are po:Lycarbonate diols having a molecular weigllt oE about 200 to 500.
~ preferrecl polycarbonate diol is an oligomer reaction product oi l,fi-hexanetlLol and a carbonate, which has an average molecular weight oi about 400 to 440. The polycarbor.ate diols are preEerably synthesized itl accord-ance with the teachings of U.S. Patent No. 4,160,853.
The triisocyanate preEerably has a molecular wc!:igllt greater than 500, preferably greater than 56n. Prererrecl tri:isocyan.ltes are reLat:ively nonvolatile. Examples of pre~errecl trilsocyanates inclucle a tr:iiso-cy.ltlurclte oE isopllorolle~ dii.soc.lllate allcl a ~:r:iisocy.ltlate hiuret o~ l,G-hexamethylene diisocyanate. ~ pre~erred triiosocyanurate oE isophorone diisocyanate is available as T-1890s* from Thorson Chemical Company, New York, and a pre~erred tr:Lisocyanate biuret of 1,6-hexamethylene diisocyanate is available as Desmodur* N from Mobay Chemical Corporation, Pittsbllrgh, Pennsylvania.
The aliphatic diisocyanate and polyol are preferably mixed together in a solvent under vacuum in a reaction kettle until the reaction *Trade Mark ~l;2l3~
mixture is single phase and well degassed. The reaction solution further comprises a catalyst, preferably the tetrabutyl titanate which is present in the polycarbonate diol synthesized by the preferred method disclosed above. The catalyst is preferably present at a level of about 100 to 1000 parts per million.
The diisocyanate and polycarbonate diol are reacted in appropriate proportions to form an OH-terminated prepolymer. The prepolymer is then crosslinked to form an abrasion resistant polyurethane by means of the tri-isocyanate crosslinking agent. In an alternative embodiment, the polyol, diisocyanate and crosslinking agent may be added together in a one-shot polymerization reaction mixture. The reaction solution may further com-prise adhesion control additives and agents to improve weathering proper-ties such as antioxidants and ultraviolet radiation absorbers.
The polyurethane reactants may be dissolved in any solvent for the reactants, preferably methyl ethyl ketone, propylacetate, toluene, cyclohexanone and mixtures thereof. The concentration of reactants is chosen to yield a viscosity suitable for the particular application tech-nique. Preferred application techniques include flow coating and dip coat-ing, as opposed to spraying, in order to minimize volatilization. The reaction solution preferably contains a wetting agent such as a fluorocar-bon surfactant to improve the optical quality of the coating. The reaction solution preferably contains about 25 percent solids and dries to form a coating less than about 0.005 inch (0.13 millimeter) thick, preferably about 0.002 inch ~about 0.05 millimeter) thick. The ?olyurethane is typi-cally cured at temperatures from about 225 to 275F (about 107 to 135C), preferably about 250 to 275F (about 121 to 135C), for about 1 hour or longer to yield an abrasion resistant coating.
The present invention will be more fully understood from the descriptions of specific examples which follow.
3~k'~
EXAMPLE I
A hydroxy-terminated prepolymer is prepared by reacting 57 weight percent 1,6-hexanediol polycarbonate diol having an average molecu1ar weight of about 420 with 43 weight percent 4,4'-methylene-bis-(cyclohexyl isocyanate) available as Desmodur W from Mobay Chemical Corporation9 Pittsburgh, Pennsylvania. A polyurethane is prepared by reacting 81 weight percent of the prepolymer with 19 weight percent of a triisocyanurate of isophorone diisocyanate. These reactants are dissolved at a concentration of 25 weight percent in a solvent comprising equal weights of toluene and cyclohexanone. The solution further comprises 1 percent each, based on the weight of polyurethane reactants, of an antioxidant and an ultraviolet radiation stflbilizer, Irganox~1076 and Tinuvin 770 respectively, both available from CIBA-GIEGY Corporation, as well as 0.1 gram per 100 milli-liters of solution of a wecting agent, FC ~30 fluorosurfactant, available from the 3M Corporation, Minneapolis, Minnesota. The reaction mixture is coated onto a stretched acrylic sheet by flow coating, and is cured for 1 1/2 hours using infrared heaters at 250F (about 121C) to form an abrasion resistant polyurethane coating. The abrasion resistance of the coating is measured by the increase in haze resulting from 300 cycles Bayer Abrader.
Results are compared with haze measurements following abrasion of uncoated acrylic in the table below. Both coated and uncoated substrates initially exhibit about 1.6 percent ha~e as measured by a Gardner Automatic Pivotable Sphere Hazemeter with an illuminant C filter.
EXAMPLE II
A polyurethane composition is flow coated onto a transparent poly-carbonate substrate and cured as in Example I. The abrasion resistance of coated and uncoated polycarbonate substrates are compared in the table below.
r~e ~ k 3~
EXAMPLE III
A polyurethane composition is prepared from 78 weight percent of the prepolymer of Example I and 22 weight percent of a triisocyanate biuret of 1,6-hexamethylene diisocyanate. The composition further comprises the additives of Example I. The composition is applied by flow coating onto a polycarbonate sheet and cured to form an abrasion resistant coating. The abrasion resistance, measured by the haze increase after abrasion, is shown in the following table.
TABLE I
Coating Substrate % Haze*
Example I Acrylic 4.8 None Acrylic 56 Example II Polycarbonate 5.4 None Polycarbonate 70 Example III Polycarbonate 3.3 * Measured with a Gardner Automatic Pivotable Sphere Hazemeter after 300 cycles Bayer Abrader.
EXAMPLE IV
A polyureehane reaction mixture is coated onto a preformed ther-moplastic polyurethane sheet wh;ch is subsequently laminated to a glasssheet to form a bilayer laminate. The polyurethane reaction mixture com-prises 78 weight percent of the prepolymer as in Example I and 22 weight percent of a triisocyanate biuret of 1,6-hexamethylene diisocyanate dis-solved at a concentration of 25 weight percent in a solvent comprising equal weights of toluene and cyclohexanone. The reaction solution further comprises the antioxidant and ultraviolet radiation stabilizer described in Example I, along with 0.12 gram per 100 milliliters of ~he fluorosurfactant.
The reaction mixture is flow coated onto the thermoplastic polyurethane sheet, dried, and cured during ehe lamination process to form a thin, 3~
abrasion resistant crosslinked polyurethane coating on the therlDo~ stic polyurethane surface of the bilayer laminate. The lamination process is described in detail in U.S. ~atent ~o. 3,808,079 to Rieser et al.
The above examples are offered to illustrate the present invention.
Various modifications, such as the coating of other substrates, the use of other cpmponents~ applying and curing by other means, etc. are included within the scope of the present invention, which is defined by the following claim:
METHOD FOR APPLYING
ABRASION RESISTANT THIN POLYURETHANE COATINGS
Background of the Invention Field of the Invention The present invention relates generally to abrasion resistant polyurethane coatings, and more particularly to a method for applying thin polyurethane coatings.
Discussion of the Technology U.S. Patent No. 4,079,160 to Phillipson teaches an optical ele-ment, such as an eyeglass lens, formed of a typical rigid polymeric sub-strate of relatively low scratch resistance coated on at least one surface with a relatively soft, resil;ent and tough, transparent polymeric material.
Spinning techniques are disclosed to be particularly suitable for applying the coating to the lens.
U.S. Patent No. 4,174,240 to Muller teaches laminates wherein gla:3s or glass~like plastics are coated with a transparent film 0.1 to 5 millimeters thick formed from a polyurethane polyurea containing 1 to 20 percent by weight urea groups and 0.001 to 10 percent by weight lateral -COOH groups. The polyurethane polyurea films are formed by solution casting or extrusion and are subsequently laminated to the substrates by the application of heat and pressure.
Summary of the Invention The present invention involves the use of relatively soft, resilient, crosslinked polyurethanes as abrasion resistant coatings. The ~2t~
polyurethanes of the present invention are prepared from aliphatic diiso-cyanates, straight chain polycarbonate diols, and crosslinking agents such as triisocyanates. The crosslinked aliphatic polycarbonate urethane coat-ings of the present invention are applied from solutions of prepolymer and crosslinking agent which are for example flow or dip coated onto a substrate, dri,ed, and cured to preferably form a coating less than 0.005 inch (0.13 millimeter) thick, more preferably about 0.001 to 0.002 inch (0.025 to 0.05 millimeter) thick~ By using a prepolymer and a relatively nonvolatile crosslinking agent, the method of the present invention minimi7es exposure to volatile free isocyanate. Volatilization of isocyanate is Eurther minimized by employing a coatLng technique whereby the substrate to be coated ls contacted with the coating solution in a continuous liquid phase, such as in ~low or dip coating, rather than a spray. The polyurethane coatings of tlle present invention are especialLy useful in aircraft transparencies as abrasion resistant coatings, either on rigid plastic layers such as polycarbonate or acrylic, or on resilient plastic layers such as impact resistant polyurethane in a glass bilayer lamina~e~
Description of the Preferred I~Aml)o(llments _ _ _ _ _ .
~n abrasion resistant, crosslinked aliphatic polyurethane is prepared from a reaction mixture of an aliphatic organic diisocyanate, a polyol, and a high molecular weight triisocyanate. The polyol is preEerably a polycarbonate diol having a molecular weight below 500.
Tetrabutyl titanate catalyst is also preferred in accordance with ~.S.
Patent No. 4,160,853.
The diisocyanate is preferably a cycloaliphatic diisocyanate such as 4,4'~methylene-bis-(cyclohexyl isocyanate). Polyurethanes prepared from _ ~ _ al;phat:Lc lsocyall.ltes, pnrtlcularLy cyc~o<~ atic d-iisocycllla~es, I~.lve good physical and optical properties over a wide temperat-lre range, ancl are not adversely affected by ultraviolet light. In addition to the most prefer-red diisocyanate, 4~4'methylene-bis-(cyclohexyl isocyanate), other suitable aliphatic diisocyanates include 1,4-cyclohexyl diisocyanate, 4,4-isopropyli,dene-bis-(cy~lohexyl isocyanate), and other dinuclear cyclo-alipha~ic diisocyanates, preferably isophorone diisocyanate. Branched diisocyanates such as trimethylhexamethylene diisocyanate may also be used, preferably in combination with 4,4'-methylene-bis-(cyclohexyl isocyanate) or isophorone diisocyanate.
Polyols useful according to the present invention may be licluicl at room temperature or soluble in the reaction mixture. Preferred polyols are po:Lycarbonate diols having a molecular weigllt oE about 200 to 500.
~ preferrecl polycarbonate diol is an oligomer reaction product oi l,fi-hexanetlLol and a carbonate, which has an average molecular weight oi about 400 to 440. The polycarbor.ate diols are preEerably synthesized itl accord-ance with the teachings of U.S. Patent No. 4,160,853.
The triisocyanate preEerably has a molecular wc!:igllt greater than 500, preferably greater than 56n. Prererrecl tri:isocyan.ltes are reLat:ively nonvolatile. Examples of pre~errecl trilsocyanates inclucle a tr:iiso-cy.ltlurclte oE isopllorolle~ dii.soc.lllate allcl a ~:r:iisocy.ltlate hiuret o~ l,G-hexamethylene diisocyanate. ~ pre~erred triiosocyanurate oE isophorone diisocyanate is available as T-1890s* from Thorson Chemical Company, New York, and a pre~erred tr:Lisocyanate biuret of 1,6-hexamethylene diisocyanate is available as Desmodur* N from Mobay Chemical Corporation, Pittsbllrgh, Pennsylvania.
The aliphatic diisocyanate and polyol are preferably mixed together in a solvent under vacuum in a reaction kettle until the reaction *Trade Mark ~l;2l3~
mixture is single phase and well degassed. The reaction solution further comprises a catalyst, preferably the tetrabutyl titanate which is present in the polycarbonate diol synthesized by the preferred method disclosed above. The catalyst is preferably present at a level of about 100 to 1000 parts per million.
The diisocyanate and polycarbonate diol are reacted in appropriate proportions to form an OH-terminated prepolymer. The prepolymer is then crosslinked to form an abrasion resistant polyurethane by means of the tri-isocyanate crosslinking agent. In an alternative embodiment, the polyol, diisocyanate and crosslinking agent may be added together in a one-shot polymerization reaction mixture. The reaction solution may further com-prise adhesion control additives and agents to improve weathering proper-ties such as antioxidants and ultraviolet radiation absorbers.
The polyurethane reactants may be dissolved in any solvent for the reactants, preferably methyl ethyl ketone, propylacetate, toluene, cyclohexanone and mixtures thereof. The concentration of reactants is chosen to yield a viscosity suitable for the particular application tech-nique. Preferred application techniques include flow coating and dip coat-ing, as opposed to spraying, in order to minimize volatilization. The reaction solution preferably contains a wetting agent such as a fluorocar-bon surfactant to improve the optical quality of the coating. The reaction solution preferably contains about 25 percent solids and dries to form a coating less than about 0.005 inch (0.13 millimeter) thick, preferably about 0.002 inch ~about 0.05 millimeter) thick. The ?olyurethane is typi-cally cured at temperatures from about 225 to 275F (about 107 to 135C), preferably about 250 to 275F (about 121 to 135C), for about 1 hour or longer to yield an abrasion resistant coating.
The present invention will be more fully understood from the descriptions of specific examples which follow.
3~k'~
EXAMPLE I
A hydroxy-terminated prepolymer is prepared by reacting 57 weight percent 1,6-hexanediol polycarbonate diol having an average molecu1ar weight of about 420 with 43 weight percent 4,4'-methylene-bis-(cyclohexyl isocyanate) available as Desmodur W from Mobay Chemical Corporation9 Pittsburgh, Pennsylvania. A polyurethane is prepared by reacting 81 weight percent of the prepolymer with 19 weight percent of a triisocyanurate of isophorone diisocyanate. These reactants are dissolved at a concentration of 25 weight percent in a solvent comprising equal weights of toluene and cyclohexanone. The solution further comprises 1 percent each, based on the weight of polyurethane reactants, of an antioxidant and an ultraviolet radiation stflbilizer, Irganox~1076 and Tinuvin 770 respectively, both available from CIBA-GIEGY Corporation, as well as 0.1 gram per 100 milli-liters of solution of a wecting agent, FC ~30 fluorosurfactant, available from the 3M Corporation, Minneapolis, Minnesota. The reaction mixture is coated onto a stretched acrylic sheet by flow coating, and is cured for 1 1/2 hours using infrared heaters at 250F (about 121C) to form an abrasion resistant polyurethane coating. The abrasion resistance of the coating is measured by the increase in haze resulting from 300 cycles Bayer Abrader.
Results are compared with haze measurements following abrasion of uncoated acrylic in the table below. Both coated and uncoated substrates initially exhibit about 1.6 percent ha~e as measured by a Gardner Automatic Pivotable Sphere Hazemeter with an illuminant C filter.
EXAMPLE II
A polyurethane composition is flow coated onto a transparent poly-carbonate substrate and cured as in Example I. The abrasion resistance of coated and uncoated polycarbonate substrates are compared in the table below.
r~e ~ k 3~
EXAMPLE III
A polyurethane composition is prepared from 78 weight percent of the prepolymer of Example I and 22 weight percent of a triisocyanate biuret of 1,6-hexamethylene diisocyanate. The composition further comprises the additives of Example I. The composition is applied by flow coating onto a polycarbonate sheet and cured to form an abrasion resistant coating. The abrasion resistance, measured by the haze increase after abrasion, is shown in the following table.
TABLE I
Coating Substrate % Haze*
Example I Acrylic 4.8 None Acrylic 56 Example II Polycarbonate 5.4 None Polycarbonate 70 Example III Polycarbonate 3.3 * Measured with a Gardner Automatic Pivotable Sphere Hazemeter after 300 cycles Bayer Abrader.
EXAMPLE IV
A polyureehane reaction mixture is coated onto a preformed ther-moplastic polyurethane sheet wh;ch is subsequently laminated to a glasssheet to form a bilayer laminate. The polyurethane reaction mixture com-prises 78 weight percent of the prepolymer as in Example I and 22 weight percent of a triisocyanate biuret of 1,6-hexamethylene diisocyanate dis-solved at a concentration of 25 weight percent in a solvent comprising equal weights of toluene and cyclohexanone. The reaction solution further comprises the antioxidant and ultraviolet radiation stabilizer described in Example I, along with 0.12 gram per 100 milliliters of ~he fluorosurfactant.
The reaction mixture is flow coated onto the thermoplastic polyurethane sheet, dried, and cured during ehe lamination process to form a thin, 3~
abrasion resistant crosslinked polyurethane coating on the therlDo~ stic polyurethane surface of the bilayer laminate. The lamination process is described in detail in U.S. ~atent ~o. 3,808,079 to Rieser et al.
The above examples are offered to illustrate the present invention.
Various modifications, such as the coating of other substrates, the use of other cpmponents~ applying and curing by other means, etc. are included within the scope of the present invention, which is defined by the following claim:
Claims (15)
IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method for applying an abrasion resistant polyurethane coating onto a surface of a substrate while minimizing volatilization of free isocyanate comprising the steps of:
a. reacting an aliphatic diisocyanate with excess polyol to form a hydroxy-terminated prepolymer;
b. adding to said prepolymer a triisocyanate crosslinking agent having a molecular weight greater than 500;
c. applying said prepolymer and triisocyanate mixture in a solvent to the surface of the substrate by contacting said surface with said solution in a continuous liquid phase;
d. evaporating said solvent; and e. reacting said prepolymer and triisocyanate to form a crosslinked polyurethane coating.
a. reacting an aliphatic diisocyanate with excess polyol to form a hydroxy-terminated prepolymer;
b. adding to said prepolymer a triisocyanate crosslinking agent having a molecular weight greater than 500;
c. applying said prepolymer and triisocyanate mixture in a solvent to the surface of the substrate by contacting said surface with said solution in a continuous liquid phase;
d. evaporating said solvent; and e. reacting said prepolymer and triisocyanate to form a crosslinked polyurethane coating.
2. The method according to Claim 1, wherein a continuous stream of solution is flowed onto the surface of the substrate.
3. The method according to Claim 1, wherein the substrate is dipped into the solution.
4. The method according to Claim 2, wherein the aliphatic diisocyanate is a cycloaliphatic diisocyanate and the polyol is a polyester polyol.
5. The method according to Claim 3, wherein the aliphatic diisocyanate is a cycloaliphatic diisocyanate and the polyol is a polyester polyol.
6. The method according to claim 4, wherein the cycloaliphatic diisocyanate is 4,4'-methylene-bis-(cyclohexyl isocyanate), the polyol is a polycarbonate diol, and the triisocyanate has a molecular weight greater than 560.
7. The method according to claim 5, wherein the cycloaliphatic diisocyanate is 4,4'-methylene-bis-(cyclohexyl isocyanate), the polyol is a polycarbonate diol, and the triisocyanate has a molecular weight greater than 560.
8. The method according to claim 6, wherein the prepolymer and triisocyanate are dissolved in a solvent selected from the group consisting of methyl ethyl ketone, propylacetate, toluene, cyclohexanone and mixtures thereof.
9. The method according to claim 7, wherein the prepolymer and triisocyanate are dissolved in a solvent selected from the group consisting of methyl ethyl ketone, propylacetate, toluene, cyclohexanone and mixtures thereof.
10. The method according to claim 8 or 9, wherein the prepolymer and triisocyanate are dissolved at a concentration of about 20 to 30 weight percent in a solvent comprising a mixture of toluene and cyclohexanone.
11. The method according to claim 8, wherein said solution further comprises a wetting agent.
12. The method according to claim 9, wherein said solution further comprises a wetting agent.
13. The method according to claim 11, wherein said wetting agent is a fluorocarbon surfactant.
14. The method according to claim 12, wherein said wetting agent is a fluorocarbon surfactant.
15. The method according to claim 13 or 14, wherein the crosslinked polyurethane coating has a thickness less than about 0.005 inch (about 0.13 millimeter).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/394,556 US4435450A (en) | 1982-07-02 | 1982-07-02 | Method for applying abrasion resistant thin polyurethane coatings |
| US394,556 | 1982-07-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1200161A true CA1200161A (en) | 1986-02-04 |
Family
ID=23559450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000429930A Expired CA1200161A (en) | 1982-07-02 | 1983-06-08 | Method for applying abrasion resistant thin polyurethane coatings |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4435450A (en) |
| JP (1) | JPS5922917A (en) |
| CA (1) | CA1200161A (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3685211D1 (en) * | 1985-08-20 | 1992-06-11 | Smith & Nephew | COATED ITEMS AND METHOD FOR THEIR PRODUCTION. |
| US5039458A (en) * | 1987-12-21 | 1991-08-13 | W. R. Grace & Co.-Conn. | Method of making a hydrophilic, biocompatible, protein non-adsorptive contact lens |
| US5880171A (en) * | 1989-05-01 | 1999-03-09 | 2C Optics, Inc. | Fast curing polymeric compositions for ophthalmic lenses and apparatus for preparing lenses |
| US5278243A (en) * | 1992-01-14 | 1994-01-11 | Soane Technologies, Inc. | High impact resistant macromolecular networks |
| DE4010485A1 (en) * | 1990-03-31 | 1991-10-02 | Ver Glaswerke Gmbh | METHOD FOR PRODUCING A PLATE OR FILM FROM POLYCARBONATE WITH A SOFT SCRATCH-PROOF COATING |
| US5939188A (en) * | 1991-07-15 | 1999-08-17 | Pilkington Aerospace, Inc. | Transparent coating systems for improving the environmental durability of transparency substrates |
| US5318827A (en) * | 1992-06-15 | 1994-06-07 | The Dow Chemical Company | Carbonate polymer laminate structure |
| DE4243798A1 (en) * | 1992-12-23 | 1994-06-30 | Wolff Walsrode Ag | Multi-layer polyurethane film and its use in the manufacture of packaging for light-sensitive material |
| US5648149A (en) * | 1994-03-29 | 1997-07-15 | Ppg Industries, Inc. | Adhesion of thermoset polyurethane to rigid transparent substrates |
| US5877254A (en) * | 1996-07-22 | 1999-03-02 | Film Specialties, Inc. | Scratch-resistant anti-fog coating composition incorporating isocyanate-reactive surfactants |
| US5776548A (en) * | 1996-11-05 | 1998-07-07 | Ppg Industries, Inc. | Primer for promoting adhesion of polyurethane to a metal oxide coating |
| US5994452A (en) * | 1996-11-05 | 1999-11-30 | Ppg Industries Ohio, Inc. | Primer for promoting adhesion of electroconductive metal oxide coating to plastic substrates |
| US5840429A (en) * | 1996-11-05 | 1998-11-24 | Ppg Industries, Inc. | Aircraft transparency |
| CA2214594C (en) * | 1996-11-05 | 2002-11-26 | Robert M. Hunia | Improved aircraft transparency |
| US7937023B2 (en) * | 2004-07-09 | 2011-05-03 | Eastman Kodak Company | Method and a composition for producing an undercoat layer using dialkyl malonate blocked isocyanates (for electrophotographic applications) |
| KR101331040B1 (en) * | 2005-08-24 | 2013-11-20 | 더 아울드 컴퍼니 | Coated display pieces and method of producing same |
| JP2007238797A (en) * | 2006-03-09 | 2007-09-20 | Polymatech Co Ltd | Paint composition and article |
| US7998529B2 (en) | 2007-10-10 | 2011-08-16 | Ppg Industries Ohio, Inc. | Methods for making polymeric substrates comprising a haze-free, self-healing coating and coated substrates made thereby |
| US7939598B2 (en) * | 2007-12-12 | 2011-05-10 | Bayer Materialscience Ag | Polyisocyanate mixtures comprising cycloaliphatic structural elements |
| US20100096062A1 (en) * | 2008-09-16 | 2010-04-22 | Serigraph, Inc. | Supported Article for Use in Decorating a Substrate |
| US9957414B2 (en) | 2014-02-19 | 2018-05-01 | Ppg Industries Ohio, Inc. | Abrasion resistant polyurethane coating, coated article and method of manufacturing the same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1010311A (en) | 1909-05-01 | 1911-11-28 | Edison Inc Thomas A | Sound-reproducer. |
| US4045269A (en) | 1975-12-22 | 1977-08-30 | Sierracin Corporation | Transparent formable polyurethane polycarbonate lamination |
| US4064194A (en) | 1976-05-28 | 1977-12-20 | Scm Corporation | High solids urethane coatings |
| US4174240A (en) | 1976-10-01 | 1979-11-13 | Bayer Aktiengesellschaft | Novel transparent polyurethane polyureas for lamination of glazing materials |
| US4079160A (en) | 1977-02-07 | 1978-03-14 | Joseph Philipson | Abrasion-resistant optical element |
| DE2842805A1 (en) | 1978-09-30 | 1980-04-10 | Bayer Ag | COATING MEASURES |
| DE2906113C2 (en) | 1979-02-17 | 1985-06-13 | Fa. Carl Freudenberg, 6940 Weinheim | Use of finely dispersed polyurethane ureas as a heat seal adhesive for the production of heat sealable interlining materials |
| US4343839A (en) | 1980-12-15 | 1982-08-10 | Ashland Oil, Inc. | Vapor permeation curable polyester resin coating compositions for flexible substrates |
-
1982
- 1982-07-02 US US06/394,556 patent/US4435450A/en not_active Expired - Lifetime
-
1983
- 1983-06-08 CA CA000429930A patent/CA1200161A/en not_active Expired
- 1983-07-01 JP JP58120926A patent/JPS5922917A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| US4435450A (en) | 1984-03-06 |
| JPH0326693B2 (en) | 1991-04-11 |
| JPS5922917A (en) | 1984-02-06 |
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