CN108473655B - Branched polyester-urethane resins and coatings comprising the same - Google Patents

Branched polyester-urethane resins and coatings comprising the same Download PDF

Info

Publication number
CN108473655B
CN108473655B CN201680073282.5A CN201680073282A CN108473655B CN 108473655 B CN108473655 B CN 108473655B CN 201680073282 A CN201680073282 A CN 201680073282A CN 108473655 B CN108473655 B CN 108473655B
Authority
CN
China
Prior art keywords
polyester
urethane resin
urethane
uncured
coating
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.)
Active
Application number
CN201680073282.5A
Other languages
Chinese (zh)
Other versions
CN108473655A (en
Inventor
F·西阿乔
A·安托纳希
E·博纳罗
S·肖赫
W·科莱格尔
B·塞莱尔
J·卡麦拉诺
D·L·辛格
J·E·施温德曼
S·斯瓦鲁普
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PPG Industries Ohio Inc
Original Assignee
PPG Industries Ohio Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US14/967,763 external-priority patent/US10035872B2/en
Application filed by PPG Industries Ohio Inc filed Critical PPG Industries Ohio Inc
Publication of CN108473655A publication Critical patent/CN108473655A/en
Application granted granted Critical
Publication of CN108473655B publication Critical patent/CN108473655B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C08G18/28—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
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
    • 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
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
    • C09D5/4465—Polyurethanes

Abstract

Uncured branched polyester-urethane resins are disclosed which are prepared by free radical polymerization of unsaturated polyester prepolymers having polyol segments, unsaturated polycarboxylic acids and/or anhydrides and/or esters thereof and urethane segments, wherein the polymerization occurs primarily through reaction of the unsaturation. Also disclosed are coatings comprising the resin, and substrates at least partially coated with the coatings.

Description

Branched polyester-urethane resins and coatings comprising the same
Cross Reference to Related Applications
This application is a continuation-in-part application entitled "branched polyester polymers and coatings comprising same" filed 4/1/2010, U.S. patent application serial No. 12/752,570.
Technical Field
The present invention relates to uncured branched polyester-urethane resins prepared by free radical polymerization of the double bonds of unsaturated polyester-urethane prepolymers. The invention further relates to a coating comprising the polyester-urethane resin and a substrate coated with the coating.
Background
In the automotive industry, it is often desirable to apply protective and/or decorative coatings to vehicles. Such coatings may, for example, provide resistance to abrasive chipping by dirt and debris on the road, such as sand and gravel, which can lead to unsightly cracking of the vehicle paint. Coating compositions having acceptable chip resistance and decorative properties are desired.
Summary of The Invention
The present invention relates to an uncured branched polyester-urethane resin prepared by free radical polymerization of the double bonds of an unsaturated polyester-urethane prepolymer, the resin comprising: a) a polyol segment; b) unsaturated polycarboxylic acids and/or anhydrides and/or esters thereof; and c) a urethane segment. Coatings comprising such polyester-urethane resins, as well as substrates at least partially coated with such coatings, are also within the scope of the present invention.
The present invention further relates to a method of forming a multi-layer coating system on a substrate, the method comprising:
forming a first basecoat layer over at least a portion of the substrate by depositing a first basecoat composition over at least a portion of the substrate;
optionally, drying or curing the first basecoat layer;
forming a second basecoat layer over at least a portion of the first basecoat layer by depositing a second basecoat composition directly over at least a portion of the first basecoat layer, the second basecoat composition being the same or different than the first basecoat composition;
optionally, drying or curing the second basecoat layer; and
curing any uncured coating;
wherein at least one of the first and/or second lacquer compositions comprises a coating composition incorporating a polyester-urethane resin.
The present invention provides an uncured branched polyester-urethane resin prepared by:
a) free radical polymerization of the double bonds of at least one unsaturated polyester prepolymer having hydroxyl functionality to form a polyester polymer, and
b) reacting the polyester polymer of step a) with an isocyanate,
wherein the polyester prepolymer comprises:
i) a polyol segment; and
ii) unsaturated polycarboxylic acids and/or anhydrides and/or ester segments.
The present invention also provides an uncured branched polyester-urethane resin prepared by free radical polymerization of double bonds of a first unsaturated polyester prepolymer and double bonds of a second unsaturated polyester prepolymer, wherein each prepolymer independently comprises:
a) a polyol segment; and
b) unsaturated polycarboxylic acids and/or anhydrides and/or ester segments; and wherein at least one of the unsaturated polyester prepolymers comprises urethane segments; and wherein the polyester prepolymers are the same or different.
Detailed Description
The present invention relates to uncured branched polyester-urethane resins, which generally comprise a reaction product comprising a polyol segment, an unsaturated polycarboxylic acid and/or anhydride and/or ester thereof, and a urethane segment. The free radical initiator is used to initiate polymerization of the unsaturation of the unsaturated polyester-urethane prepolymer, thereby producing an uncured branched polyester-urethane resin. The branched polyester-urethane resin is uncured or otherwise "curable" and/or "crosslinkable", meaning that it can be crosslinked with another compound to form a cured coating, but is not itself a cured coating. That is, the polyester-urethane polymer has a functionality that will react with a functionality on another compound, such as a crosslinker. The reaction of the unsaturation of the prepolymer produces an uncured, crosslinkable branched polyester-urethane resin. For clarity, such polyester-urethanes are polymeric resins. It is not a cured coating. Thus, the present invention is distinct from techniques that react unsaturated sites on monomers and/or polymers to produce curing of coatings.
Polyester-urethane prepolymers are prepared by reacting one or more polyols with one or more unsaturated polycarboxylic acids/anhydrides and with one or more isocyanates.
As used herein, "polyol" and like terms refer to compounds having two or more hydroxyl groups. The polyol used to form the polyol segment or "remainder of the polyol" is sometimes referred to herein as a "polyol segment monomer". "residual moiety" refers to a portion or segment of a molecule derived from a particular monomer. For example, "the remainder of the polyol" refers to the portion derived from the polyol monomer. The polyols may also be selected to impart hardness or softness to the prepolymer, however, the polyols used and the amounts of each should be selected so that the unsaturated prepolymer, when reacted, produces a branched polyester having a desired glass transition temperature (Tg). The polyol may have 2 to 36 atoms. Suitable polyols for use in the present invention may be any polyol known for use in the preparation of polyesters. Examples include, but are not limited to, alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, and neopentyl glycol; hydrogenated bisphenol a; cyclohexanediol; propylene glycol including 1, 2-propylene glycol, 1, 3-propylene glycol, butylethylpropylene glycol, 2-methyl-1, 3-propylene glycol and 2-ethyl-2-butyl-1, 3-propylene glycol; butanediol, including 1, 4-butanediol, 1, 3-butanediol, and 2-ethyl-1, 4-butanediol; pentanediol, including trimethylpentanediol and 2-methylpentanediol; cyclohexanedimethanol; hexylene glycols, including 1, 6-hexanediol; caprolactone diol (e.g., the reaction product of epsilon-caprolactone with ethylene glycol); a hydroxyalkylated bisphenol; polyether glycols such as poly (butylene oxide) glycol; trimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, trimethylolbutane, dimethylolcyclohexane, glycerol, and the like. Suitable unsaturated polyols for use in the present invention can be any unsaturated alcohol containing two or more hydroxyl groups. Examples include, but are not limited to, trimethylolpropane monoallyl ether, trimethylolethane monoallyl ether, and prop-1-ene-1, 3-diol. The polyol segment may also include some monohydric alcohols, for example up to 10 or 5 weight percent based on the total weight of the polyol segment. The polyol segment may be saturated.
The unsaturated polyester-urethane prepolymer further comprises an unsaturated polycarboxylic acid, anhydride and/or ester thereof, or a residue derived therefrom. Suitable unsaturated polyacids for use in the present invention can be any unsaturated carboxylic acid containing two or more carboxyl groups and/or esters and/or anhydrides thereof. Examples include, but are not limited to, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and mesaconic acid and/or esters and/or anhydrides thereof. Particularly suitable unsaturated polybasic acids are maleic acid, maleic anhydride or C of maleic acid1-C6An alkyl ester. The unsaturated polycarboxylic acid/anhydride/ester may comprise 3 to 10 wt%, such as 4 to 7 wt% of the polyester-urethane prepolymer.
As previously mentioned, the unsaturated polyester-urethane prepolymer contains urethane segments. "urethane segment" will be understood to have a urethane (NHCOO) functional group. Although at least one of the polyester-urethane prepolymers used according to the present invention has a urethane segment, more than one or all of the prepolymers may have such a urethane segment. It will be appreciated that the use of at least one polyester-urethane prepolymer having urethane segments will result in urethane segments being present in the final polyester-urethane resin, and thus also in the coating formed from the resin. The urethane segments may constitute from 5 to 45 weight percent, based on the total weight of the polyester-urethane prepolymer, such as from 10 to 25 weight percent.
The urethane segments may be incorporated into the polyester-urethane prepolymer by reaction with an isocyanate having an (NCO) group or isocyanate functionality. The isocyanate may have 4 to 25 carbon atoms. Suitable isocyanates include aromatic and aliphatic polyisocyanates, including cycloaliphatic polyisocyanates, representative examples include diphenylmethane-4, 4' -diisocyanate (MDI), 2, 4-or 2, 6-Toluene Diisocyanate (TDI), including mixtures thereof, p-phenylene diisocyanate, tetramethylene and hexamethylene diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, isophorone diisocyanate, mixtures of phenylmethane-4, 4' -diisocyanate and polymethylene polyphenylisocyanate. Higher polyisocyanates such as triisocyanates, e.g., triphenylmethane-4, 4',4 "-triisocyanate, can be used. According to the invention, the isocyanates may be blocked or unblocked. Isocyanate prepolymers prepared in combination with polyols such as neopentyl glycol and trimethylolpropane and polymer polyols such as polycaprolactone diols and triols (NCO/OH equivalent ratio can be greater than 1) can also be used.
According to the present invention, the isocyanate may be reacted with a polyol segment and an unsaturated polycarboxylic acid/anhydride/ester segment, or with a polyester prepolymer before reaction. The polyester-urethane prepolymer may also be formed by reacting together all of the polyol segment, the unsaturated polycarboxylic acid/anhydride/ester segment, and the isocyanate. As used herein, "polyester prepolymer" refers to the reaction product of polyol segments and unsaturated polycarboxylic acid/anhydride/ester segments. For polyester prepolymers, the ratio of reactive hydroxyl groups (OH) on the polyol segment to acid groups on the unsaturated polycarboxylic acid/anhydride/ester segment may be 2: 0.5,2: 1.5 or even higher. The higher the ratio, the higher the molecular weight of the reaction product. The reaction product polyester prepolymer has hydroxyl-terminated functionality due to the use of excess polyol.
As will be discussed in detail below, the polyester-urethane resin may be prepared using either a solvent-based system or a water-based system. For solvent-based systems, the isocyanate may be reacted with the polyol segment or the hydroxyl functionality of the polyester prepolymer such that the ratio of isocyanate functional groups (NCO) to hydroxyl groups (OH) of the polyester-urethane prepolymer is 1: 2-1: 1.5. for water-based systems, the polyester-urethane prepolymer may be prepared such that it contains unreacted OH functionality and unreacted NCO functionality such that it can be further reacted with a hydroxyl group-containing carboxylic acid to become acid-functional. The acid-functionalized prepolymer may then be neutralized with a base, dispersed and polymerized in water. Thus, the polyester-urethane prepolymer may have 10% to 30% unreacted NCO groups and 70% to 90% unreacted OH groups. Typically, the reaction with the isocyanate is carried out at a temperature of from 50 ℃ to 120 ℃. According to the invention, the reaction with the isocyanate can be carried out in any non-alcoholic organic solvent. Suitable non-alcoholic organic solvents include butyl acetate, amyl acetate, methyl isobutyl ketone, methyl ethyl ketone, propylene glycol monomethyl ether or mixtures thereof.
According to the present invention, the resulting unsaturated polyester-urethane prepolymer will have hydroxyl end functionality and unsaturation. The average functionality of the unsaturation of the polyester-urethane prepolymer may range from 1 to 5, such as 2 to 4, and may be 2 or higher. While not wishing to be bound by such a mechanism, it is believed that the higher hydroxyl functionality provides more reactive and/or crosslinking sites for the resulting resin and any coating containing such resin to react with the crosslinker and/or adjacent coating layers in the coating composition of the invention, thereby providing better intercoat adhesion between two adjacent coating layers, better chip resistance and sag resistance properties.
The unsaturated polyester-urethane prepolymer may further comprise one or more monomers that contribute to the overall properties of the polyester, including "flexibility", stain resistance, durability, chemical resistance, and/or mechanical resistance. For example, one or more monomers contributing "soft segments" may be combined with one or more poly(s)The polyhydric alcohol is used with one or more unsaturated polycarboxylic acids/anhydrides/esters. As used herein, "soft segment" and similar terms refer to a monomer or residue thereof or a mixture thereof that contributes flexibility to the prepolymer and can help achieve a desired Tg and/or viscosity for the branched polyester-urethane resin. The soft segment may be, for example, the residue of a polyacid. As used herein, "polyacid" and similar terms refer to compounds having two or more acid groups, including esters and/or anhydrides of acids. Such acids may include, for example, straight chain acids that impart flexibility. Examples include, but are not limited to, saturated polybasic acids such as adipic acid, azelaic acid, sebacic acid, succinic acid, glutaric acid, sebacic acid, dodecanedioic acid and their esters and anhydrides. Suitable monoacids include C1-C18Aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, caproic acid, oleic acid, linoleic acid, undecanoic acid, lauric acid, isononanoic acid, other fatty acids, and hydrogenated fatty acids of naturally occurring oils; and/or esters and/or anhydrides of any of these.
The uncured branched polyester-urethane prepolymer of the present invention may further comprise a hard segment. As used herein, "hard segment" and similar terms refer to a monomer or residue thereof that contributes rigidity to a prepolymer rather than flexibility. The hard segment may be, for example, the residue of a polyacid. The polyacid may be an aromatic acid or a cycloaliphatic acid, suitable examples of which include, but are not limited to, phthalic acid, isophthalic acid, 5-tert-butylisophthalic acid, tetrachlorophthalic acid, tetrahydrophthalic acid, naphthalenepolycarboxylic acid, terephthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, dimethylterephthalate, cyclohexanedicarboxylic acid, chlorendic anhydride, 1, 3-cyclohexanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, tricyclodecanepolycarboxylic acid, endomethylenetetrahydrophthalic acid, endoethylenehexahydrophthalic acid, cyclohexanetetracarboxylic acid, cyclobutanetetracarboxylic acid and esters and anhydrides thereof, and/or combinations thereof. Monomers that contribute to the hard segment are sometimes referred to herein as "hard segment monomers". Thus, one skilled in the art would need to determine the acid and the amount of each acid used to impart the desired flexibility or rigidity and feel to the final coating, as well as other desired properties such as stain resistance.
Other monomer components may also be used to form the prepolymer to impart one or more additional properties to the branched polyester-urethane resin and/or the coating comprising the same. For example, phthalic anhydride may be included, such as in an amount of 2-20% by weight of the prepolymer; phthalic anhydride can impart greater stain resistance to the coating. Fatty diacids can increase hydrophobicity, while polyethers such as poly-THF can make branched polyester-urethane resins more hydrophilic. Diene monomers, such as butadiene, may also contribute to the soft feel, chemical resistance and/or flexibility, such as dicyclopentadiene, which contributes to durability and rubber-like feel.
According to the present invention, the unsaturated polyester-urethane prepolymer is polymerized in the presence of a free radical initiator. In the radical polymerization, any radical initiator typically used for initiating polymerization of unsaturated compounds containing double bonds may be used. For example, the free radical initiator may be an azo initiator or a peroxide initiator, such as t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy benzoate or dibenzoyl peroxide. Such free radical initiators are commercially available from Arkema as LUPEROX 26. The ratio of initiator to unsaturated acid/anhydride/ester may vary depending on the degree of branching of the polyester chain desired. For example, the molar ratio of initiator to average number of double bonds per unsaturated acid/anhydride/ester chain may be from 0.001 to 1.0, such as from 0.01 to 0.9 or from 0.5 to 1.
Thus, the unsaturation from one acid/anhydride moiety reacts with the unsaturation of another in the reaction product. The result is a branched polyester polymer. At least some, if not all, of the branches have terminal hydroxyl groups. Depending on the starting materials used, pendant functionalities may also be present in the branched polyester. Typically, when an initiator is used in combination with an unsaturated acid/anhydride/ester, a linear polymer is obtained. Thus, it is very surprising and unexpected that branched polyester-urethane resins are obtained according to the present invention. It is to be understood that in the present invention, branching is primarily obtained by reaction of unsaturation. By using tri-or tetra-hydric alcohols, a small amount of branching can be contributed, but the amount of such compounds should be selected to avoid gelation. It will be appreciated that the present method of obtaining branching by polymerization of unsaturation using polycarboxylic acids and polyesters derived therefrom is very unique when compared to conventional branched polyester-urethane resins such as those prepared by using trihydric or tetrahydric alcohols.
The initiator may be added at different times and in different proportions, depending on the degree of polymerization desired to be controlled. For example, the entire free radical initiator may be added at the beginning of the reaction, the initiator may be divided into portions and the portions added at intervals during the reaction, or the initiator may be added as a continuous feed. It will be appreciated that adding initiator at set intervals or continuously fed will result in a more controlled process than adding all initiator initially.
Regardless of the manner in which the polyester-urethane prepolymer is prepared, whether the polyester prepolymer is formed first, or the polyol segments and polycarboxylic acid/anhydride/ester are reacted directly with the isocyanate, and how and when the initiator, etc., is added, the resulting branched polyester-urethane resins are actually a mixture of polyester-urethane resins having a variety of degrees of unsaturation, chain lengths, branching, etc. Some of the resulting products may even be monoesters, but are still encompassed by the term "polyester" as used herein.
The temperature at which the free radical polymerization reaction is carried out can vary depending on such factors as the composition of the unsaturated acid/anhydride/ester, polyol segment monomer, urethane segment, initiator, solvent, and properties desired for the polyester. Typically, free radical polymerization is carried out at a temperature of 50 ℃ to 150 ℃. In typical polymerizations, such as acrylics, higher temperatures result in higher free radical initiator concentrations, which in turn results in polymerization of more chains, each having a relatively lower molecular weight. In the system of the present invention, it has surprisingly been found that, in particular when using a maleic species, the higher the initiator concentration, the higher the molecular weight of the resulting polymer. This is a surprising result, since the person skilled in the art would not have expected the polymerization of the invention to take place. However, when polymerization occurs in the solvent phase, too much initiator can lead to gelation. The polyester-urethane resin of the present invention may be non-gelling.
Although the polymerization can be carried out in any manner, for ease of handling, the radical polymerization can be carried out using a solution of unsaturated acid/anhydride, urethane segment and polyol segment monomers. Free radical polymerization can be carried out in solvent-based or water-based systems. Any solvent can be used as long as it can dissolve the components including the radical initiator to an extent sufficient for polymerization to effectively occur. Typical examples of suitable solvents include butylene glycol, propylene glycol monomethyl ether, glycol diether, methoxypropyl acetate, and xylene. The preparation of polyester-urethane resins in a solvent is sometimes referred to herein as a "solvent-based system," meaning that more than 50%, such as up to 100%, of the solvent is organic, and less than 50%, such as less than 20%, less than 10%, less than 5%, or less than 2%, of the solvent is water.
Alternatively, the polyester-urethane resin may be prepared in a water-based system. An "aqueous-based system" is a system in which more than 50%, such as up to 100%, of the solvent is water, and less than 50%, such as less than 20%, less than 10%, less than 5%, or less than 2%, of the solvent is an organic solvent. If the unsaturated polyester-urethane prepolymer has sufficient carboxylic acid groups, it can be converted to a water-dilutable material by neutralization or partial neutralization with a suitable base, followed by the addition of water. Non-limiting examples of suitable bases for neutralization include dimethylethanolamine, triethylamine, and 2-amino-2-methylpropanol. The aqueous material may then be polymerized using free radicals as described above. Alternatively, the unsaturated polyester prepolymer may be mixed with a surfactant and/or polymeric stabilizer material and then mixed with water prior to the aforementioned free radical polymerization. It will also be apparent to those skilled in the art that these aqueous mixtures may contain additional organic cosolvents, examples of which include, but are not limited to, butanediol, butyl diglycol, and propylene glycol monomethyl ether. Such organic co-solvents are commercially available as PROGLYDE DMM from The Dow Chemical Company.
The present invention has been described as preparing a polyester-urethane prepolymer by reacting an isocyanate with a polyol segment and the unsaturated polycarboxylic acid/anhydride/ester segment, or with a polyol ester prepolymer, followed by polymerization by free radical polymerization. The polyester-urethane resin may also be formed by reacting polyol segments and unsaturated polycarboxylic acid/anhydride/ester segments to form at least one polyester prepolymer; and polymerizing the at least one unsaturated polyester prepolymer by free radical polymerization of the double bonds to form the hydroxyl functional polyester polymer. The polyester polymer may have an equivalent ratio of hydroxyl (OH) groups to isocyanate (NCO) groups of greater than 1. The polyester polymer may then be reacted with an isocyanate to form a polyester-urethane polymer. The polyester-urethane polymer may be prepared such that it may have an excess of NCO functionality. The excess NCO functionality allows the polyester-urethane polymer to be reacted with a hydroxyl group-containing carboxylic acid and neutralized with a base prior to dispersion in an aqueous medium.
In solvent-based or water-based systems, the resulting polyester may be solid or liquid.
As described above, the polyester-urethane polymer of the present invention is formed by double bond radical polymerization of an unsaturated polyester prepolymer containing terminal hydroxyl groups. According to the present invention, two or more different unsaturated polyester-urethane prepolymers can be reacted together. As used herein, "different" means that one or more components used in two or more unsaturated polyester-urethane prepolymers and/or the amount of one or more components used in two or more unsaturated polyester-urethane prepolymers may be different. For example, the polyester-urethane polymer according to the present invention may be prepared by reacting a polyester-urethane prepolymer comprising the same components. The polyester-urethane resin may be prepared by reacting two or more polyester-urethane prepolymers formed from different components. That is, a first polyester prepolymer containing terminal hydroxyl groups and a second polyester prepolymer containing terminal hydroxyl groups are reacted with an isocyanate; the components used to prepare the first and second prepolymers may be different or may have one or more different components. In this example, the resulting polyester-urethane resin may have random units derived from each type of prepolymer used. Thus, the present invention encompasses polyester-urethane resins prepared from the same or different urethane segments, polyol segment monomers, and/or unsaturated acids/anhydrides/esters and/or the same or different amounts of any of these. Polyester-urethane resins with different properties can be obtained using different polyester prepolymers, urethane segments, polyol segment monomers, unsaturated acids/anhydrides/esters and/or amounts. In this manner, polyester-urethane resins having desired properties can be formed by using specific components for the reaction product.
As described above, the polyester-urethane polymer is formed using free radical polymerization, wherein the unsaturation in the polycarboxylic acid/anhydride/ester moiety in the prepolymer is polymerized. The reaction may be conducted such that substantially all of the unsaturation reacts in the formation of the polyester-urethane polymer. However, in some instances, the resulting polyester-urethane polymer also contains some unsaturation. For example, the resulting polyester-urethane polymer may include sufficient unsaturation to enable the polyester-urethane polymer to react with other functional groups.
Since the branched polyester-urethane resin according to the present invention is mainly formed by radical polymerization of unsaturation in unsaturated acids/anhydrides/esters, some of the terminal hydroxyl groups will remain unreacted in the branched polyester-urethane resin of the present invention. These unreacted hydroxyl groups can then be crosslinked with another component. Thus, the present invention is distinct from techniques for forming gelled polyesters, i.e., mass networked polyesters. The polyester-urethane resins of the present invention are thermosetting after reaction with a crosslinking agent, and thus are also different from the techniques taught for thermoplastic polyesters.
In accordance with the present invention, it may be desirable to convert some or all of the hydroxyl functionality on the unsaturated polyester prepolymer, for example, before polymerization occurs, and/or some or all of the hydroxyl functionality on the branched polyester to another functionality. For example, hydroxyl groups can be reacted with a cyclic anhydride to provide acid functionality. Acid esters may also be formed.
The present invention contemplates that no unsaturated monomers other than the unsaturated polyacid/anhydride/ester of the reaction product are used. For example, the use of vinyl monomers such as (meth) acrylates, styrene, vinyl halides, and the like may be excluded. Thus, it is understood that the branched polyester-urethane resins of the present invention are not polyester/acrylic graft copolymers generally known in the art.
The polyester-urethane resin of the present invention may specifically exclude a polyester-urethane resin prepared from a prepolymer formed by reaction with an aldehyde; thus, acyl succinic acid polyesters may be specifically excluded. Similarly, the use of aldehydes in solvents may be specifically excluded.
The polyester-urethane resins of the present invention may have relatively higher molecular weight and functionality compared to conventional linear polyester-urethane resins. Typically, the ratio of the weight average molecular weight ("Mw") of the branched polyester-urethane resin of the present invention to the Mw of the unsaturated polyester-urethane resin prepolymer is from 1.2 to 100, such as from 4 or from 5 to 50.
The branched polyester-urethane resins of the present invention may have a Mw as low as 600, or may have a Mw greater than 1000, such as greater than 5000, greater than 10,000, greater than 15,000, greater than 25,000, or greater than 50,000. Molecular weights of 80,000 and 100,000 are also contemplated by the present invention. Molecular weights above 100,000 and up to 10,000,000 can be obtained. The molecular weight increase may be controlled by one or more factors such as the type and/or amount of initiator used, the amount of unsaturation on the prepolymer, the temperature, and the type and/or amount of solvent. All molecular weights disclosed herein were determined by gel permeation chromatography using polystyrene standards for calibration.
In addition to the above molecular weights, the unsaturated polyester-urethane resins of the present invention may also have relatively high functionality; in some cases, the functionality is higher than expected for conventional unsaturated polyester-urethane resins having such a molecular weight range. The average functionality of the unsaturated polyester-urethane resin may be 2.0 or higher, such as 2.5 or higher, 3.0 or higher, or even higher. As used herein, "average functionality" refers to the average number of functional groups on the branched polyester. The functionality of the branched polyester-urethane resin is measured by the number of unreacted hydroxyl groups remaining in the branched polyester-urethane resin, rather than by the unreacted unsaturation. The branched polyester-urethane polymers of the present invention may have a hydroxyl number of from 10 to 500mgKOH/g, such as from 30 to 250mgKOH/g, such as from 75 to 120mgKOH/g, as measured by ASTM method D4274. The branched polyester-urethanes of the present invention can have both a high Mw and a high functionality, for example, a Mw of 15,000 or more, such as 20,000 or more and 40,000 or more, and a functionality of 100mgKOH/g or more.
Because the polyester-urethane resins of the present invention contain functionality, they are suitable for use in coating formulations in which hydroxyl groups (and/or other functionalities) are crosslinked with other resins and/or crosslinkers typically used in coating formulations. Accordingly, the present invention further relates to a coating comprising a branched polyester-urethane resin according to the present invention and a crosslinking agent therefor. The crosslinking agent or resin or reagent may be any suitable crosslinking agent or resin known in the art and is selected to be capable of reacting with one or more functional groups on the polyester. It is to be understood that the coatings of the present invention cure by reaction of hydroxyl and/or other functional groups with the crosslinker, rather than by double bonds of the polycarboxylic acid/anhydride/ester moiety, if any such unsaturation is present in the branched polyester-urethane resin.
Non-limiting examples of suitable crosslinking agents include phenolic resins, amino resins, epoxy resins, isocyanate resins, beta-hydroxy (alkyl) amide resins, alkylated urethane resins, polyacids, anhydrides, organometallic acid functional materials, polyamines, polyamides, aminoplasts, and mixtures thereof. The crosslinking agent may be a phenolic resin comprising an alkylated phenol/formaldehyde resin having a functionality of 3 or more and a difunctional ortho-cresol/formaldehyde resin. Such cross-linking agents are commercially available from Hexion as BAKELITE 6520LB and BAKELITE 7081 LB.
Suitable crosslinking isocyanates include polyfunctional isocyanates. Examples of the polyfunctional polyisocyanate include aliphatic diisocyanates such as hexane diisocyanate and isophorone diisocyanate; and aromatic diisocyanates such as toluene diisocyanate and 4,4' -diphenylmethane diisocyanate. The polyisocyanate may be blocked or unblocked. Examples of other suitable polyisocyanates include isocyanurate trimers, uretdiones of diisocyanates, and allophanates, as well as polycarbodiimides, such as those disclosed in U.S. patent application 12/056,304 filed 3.27.2008, incorporated herein by reference in its relevant part. Suitable polyisocyanates are well known in the art and are widely commercially available. For example, suitable polyisocyanates are disclosed in U.S. patent application No. 6,316,119 at column 6, lines 19-36, which is incorporated herein by reference. Examples of commercially available polyisocyanates include DESMODUR VP2078 and DESMODUR N3390 sold by Bayer Corporation, and TOLONATE HDT90 sold by Rhodia Inc.
Suitable aminoplasts include condensates of amines and/or amides with aldehydes. For example, condensates of melamine with formaldehyde are suitable aminoplasts. Suitable aminoplasts are well known in the art. Suitable aminoplasts are disclosed, for example, in U.S. Pat. No. 6,316,119 at column 5, lines 45-55, which is incorporated herein by reference. Examples of commercially available aminoplast crosslinking resins include RESIMENE HM 2608, which is sold by Ineos Melamines, LLC.
In the preparation of the coatings of the present invention, the branched polyester-urethane polymer and the crosslinking agent may be dissolved or dispersed in a single solvent or a mixture of solvents. Any solvent capable of forming a formulation for coating onto a substrate may be used and these are well known to those skilled in the art. Typical examples include water, organic solvents and/or mixtures thereof. Suitable organic solvents include glycols, glycol ether alcohols, ketones and aromatics (e.g., xylene and toluene), acetates, petroleum ethers, naphthas and/or mixtures thereof. "acetate" includes glycol ether acetates. The solvent may be a non-aqueous solvent. By "non-aqueous solvent" and like terms is meant that less than 50% of the solvent is water. For example, less than 10% or even less than 5% or 2% of the solvent may be water. It is understood that solvent mixtures comprising less than 50% of the amount of water or no water may constitute "non-aqueous solvents". In some examples, the coating is aqueous or water-based. This means that 50% or more of the solvent is water. For example, the water-based coating may have less than 50%, such as less than 20%, less than 10%, less than 5%, or less than 2% solvent.
The present invention also contemplates coatings further comprising a curing catalyst. Any cure-destroying agent typically used to catalyze the crosslinking reaction between polyester resins and crosslinking agents, such as phenolic resins, can be used, and the catalyst is not particularly limited. Examples of such curing catalysts include phosphoric acid, alkaryl sulfonic acids, dodecylbenzene sulfonic acid, dinonyl naphthalene sulfonic acid, and dinonyl naphthalene disulfonic acid.
If desired, the coating composition may include in any of the components other optional materials known in the art for formulating coatings, such as colorants, plasticizers, abrasion resistant particles, antioxidants, hindered amine light stabilizers, UV light absorbers and stabilizers, surfactants, flow control agents, thixotropic agents, fillers, organic cosolvents, reactive diluents, catalysts, grinding carriers, and other conventional adjuvants.
As used herein, the term "colorant" refers to any substance that imparts color and/or other opacity and/or other visual effect to the composition. The colorant can be added to the composition in any suitable form, such as discrete particles, dispersions, solutions and/or flakes. A single colorant or a mixture of two or more colorants can be used in the coating of the present invention.
Examples of colorants include pigments, dyes and toners, such as those used in the paint industry and/or listed in the dry powder pigment manufacturers association (DCMA) and special effect compositions. The colorant may comprise, for example, a finely divided solid powder that is insoluble but wettable under the conditions of use. The colorant may be organic or inorganic and may be aggregated or non-aggregated. The colorant may be incorporated into the coating by grinding or simple mixing. The colorant can be incorporated into the coating by using a grind vehicle, such as an acrylic grind vehicle, the use of which will be familiar to those skilled in the art.
Examples of pigments and/or pigment compositions include, but are not limited to, carbazole dioxazine crude pigments, azo, monoazo, diazo, naphthol AS, salt forms (lakes), benzimidazolone, condensates, metal complexes, isoindolones, isoindolines and polycyclic phthalocyanines, quinacridones, perylenes, pyridones, diketopyrrolopyrroles, thioindigoids, anthraquinones, anthrapyrimidines, xanthones, pyranthrones, anthanthrones, dioxazines, triarylcarboniums, quinophthalone pigments, diketopyrrolopyrrole red ("DPPBO red"), titanium dioxide, carbon black, carbon fibers, graphite, other conductive pigments and/or fillers, and mixtures thereof. The terms "pigment" and "colored filler" may be used interchangeably.
Examples of dyes include, but are not limited to, those that are solvent-based and/or water-based, such as acid dyes, azo dyes, basic dyes, direct dyes, disperse dyes, reactive dyes, solvent dyes, sulfur dyes, mordant dyes such as bismuth vanadate, anthraquinone, perylene aluminum, quinacridone, thiazole, thiazine, azo, indigoid dyes, nitro, nitroso, oxazine, phthalocyanine, quinoline, stilbene, and triphenylmethane.
Examples of hueing agents include, but are not limited to, pigments dispersed in water-based or water-miscible vehicles such as AQUA-CHEM 896 commercially available from Degussa, Inc., CHARISMA COLORANTS and MAXITORNER INDUSTRIAL COLORANTS commercially available from Accurate Dispersions Division of Eastman Chemicals, Inc.
As noted above, the colorant can be in the form of a dispersion, including but not limited to in the form of a nanoparticle dispersion. Nanoparticle dispersions can include one or more highly dispersed nanoparticle colorants and/or colorant particles that produce a desired visible color and/or opacity and/or visual effect. Nanoparticle dispersions may include colorants, such as pigments or dyes, having a particle size of less than 150nm, for example less than 70nm, or less than 30 nm. Nanoparticles can be produced by milling a starting organic or inorganic pigment with milling media having a particle size of less than 0.5 mm. Examples of nanoparticle dispersions and methods for their preparation are described in U.S. Pat. No. 6,875,800B2, the relevant portion of which is incorporated herein by reference. Nanoparticle dispersions can also be produced by crystallization, precipitation, gas phase condensation and chemical attrition (i.e., partial dissolution). To minimize re-agglomeration of the nanoparticles in the coating, a dispersion of resin-coated nanoparticles may be used. As used herein, a "dispersion of resin-coated nanoparticles" refers to a continuous phase in which are dispersed discrete "composite particles" comprising nanoparticles and a resin coating on the nanoparticles. Examples of dispersions of resin-coated nanoparticles and methods for their preparation are described in U.S. patent publication 2005-0287348a1, filed 24.6.2004, U.S. provisional application No. 60/482,167, filed 24.6.2003, and U.S. patent application serial No. 11/337,062, filed 20.1.2006, relevant portions of which are incorporated herein by reference.
Examples of special effect compositions that may be used include pigments and/or compositions that produce one or more appearance effects, such as reflectance, pearlescence, metallic sheen, phosphorescence, fluorescence, photochromism, photosensitivity, thermochromism, goniochromism and/or color change. Other special effect compositions may provide other perceptible properties, such as opacity or texture. In a non-limiting example, the special effect composition can produce a color shift such that the color of the coating changes when the coating is viewed at different angles. Examples of color effect compositions are described in U.S. Pat. No. 6,894,086, the relevant portions of which are incorporated herein by reference. Other color effect compositions may include transparent coated mica and/or synthetic mica, coated silica, coated alumina, transparent liquid crystal pigments, liquid crystal coatings, and/or any composition in which interference is caused by refractive index differences within the material and not due to refractive index differences between the surface of the material and the air.
The present invention may also include photosensitive compositions and/or photochromic compositions that reversibly change their color when exposed to one or more light sources, which may be used in the coatings of the present invention. Photochromic and/or photosensitive compositions can be activated by exposure to radiation of a specified wavelength. When the composition is excited, the molecular structure changes and the changed structure exhibits a new color that is different from the original color of the composition. When exposure to radiation is removed, the photochromic and/or photosensitive composition can return to a quiescent state, wherein the original color of the composition is restored. The photochromic and/or photosensitive composition can be colorless in a non-excited state and exhibit color in an excited state. Complete color change can occur within milliseconds to minutes, such as 20 seconds to 60 seconds. Examples of photochromic and/or photosensitive compositions can include photochromic dyes.
In addition, the photosensitive composition and/or photochromic composition can be associated and/or at least partially bound to the polymer and/or polymeric material of the polymerizable component, such as by covalent bonding. In contrast to certain coatings in which the photosensitive composition can migrate from the coating and crystallize into the substrate, the photosensitive composition and/or photochromic composition associated and/or at least partially bound to the polymer and/or polymerizable component has minimal migration from the coating in accordance with the present invention. Examples of photosensitive and/or photochromic compositions and methods for their preparation are described in U.S. application serial No. 10/892,919, filed on 7, 16, 2004, which is incorporated herein by reference.
In general, the colorant can be present in any amount sufficient to impart the desired visual and/or color effect. The colorant may comprise 1 to 65 weight percent of the present composition, such as 3 to 40 weight percent or 5 to 35 weight percent, with weight percent based on the total weight of the composition.
"wear resistant particles" are materials that, when used in a coating, impart some wear resistance to the coating as compared to a coating lacking the particles. Suitable wear resistant particles include organic and/or inorganic particles. Examples of suitable organic particles include, but are not limited to, diamond particles such as diamond powder particles, and particles formed from carbide materials; examples of carbide particles include, but are not limited to, titanium carbide, silicon carbide, and boron carbide. Examples of suitable inorganic materials include, but are not limited to, silica, alumina, aluminum silicates, silica alumina, alkali metal aluminosilicates, borosilicate glasses, nitrides including boron nitride and silicon nitride, oxides including titanium dioxide and zinc oxide, quartz, nepheline syenite, e.g., zircon in the form of zirconia, baddeleyite, and xenolite. Particles of any size may be used, as may mixtures of different particles and/or different sized particles. For example, the particles may be microparticles having an average particle size of 0.1 to 50, 0.1 to 20, 1 to 12, 1 to 10, or 3 to 6 microns or any combination of any of these ranges. The particles may be nanoparticles having an average particle size of less than 0.1 micron, such as 0.8-500, 10-100 or 100-500 nm or any combination of these ranges.
It is to be understood that the polyester-urethane resins of the present invention and the crosslinkers therefor may form all or part of the film-forming resin of the coating. According to the present invention, one or more additional film-forming resins are used in the coating. For example, the coating composition can comprise any of a variety of thermoplastic and/or thermosetting compositions known in the art. The coating composition may be a water-based or solvent-based liquid composition, or alternatively, may be in the form of solid particles, i.e., a powder coating.
Thermosetting or curable coating compositions typically comprise a film-forming polymer or resin having functional groups that can react with itself or with a crosslinker. Other film-forming resins can be selected from, for example, acrylic polymers, polyester polymers, polyurethane polymers, polyamide polymers, polyether polymers, polysiloxane polymers, copolymers thereof, and mixtures thereof. In general, these polymers may be any of these types of polymers prepared by any method known to those skilled in the art. The polymers may be solvent-based or water-dispersible, emulsified or of limited water solubility. The functional groups on the film-forming resin may be selected from any of a variety of reactive functional groups including, for example, carboxylic acid groups, amine groups, epoxy groups, hydroxyl groups, thiol groups, carbamate groups, amide groups, urea groups, isocyanate groups (including blocked isocyanate groups), mercapto groups, and combinations thereof. Suitable mixtures of film-forming resins can also be used in the preparation of the coating compositions of the present invention.
The thermosetting coating composition typically comprises a crosslinker which may be selected from any of the crosslinkers described above. For example, the coating of the present invention comprises a thermosetting film-forming polymer or resin and a crosslinker therefor, which may be the same or different from the crosslinker used to crosslink the polyester-urethane resin. The invention may comprise the use of thermosetting film-forming polymers or resins having functional groups capable of reacting with themselves, in such a way that such thermosetting coatings are self-crosslinking.
The coating of the present invention may comprise from 1 to 100, for example from 10 to 90 or from 20 to 80 percent by weight of the polyester-urethane resin of the present invention, in percent by weight based on the total weight of coating solids. The coating composition of the present invention may also comprise 0 to 90, such as 5 to 60 or 10 to 40 weight percent of a crosslinker for the branched polyester-urethane resin, based on the weight percent of the total coating solids. If used, other components comprise from 1 wt% up to 70 wt% or more, based on the total weight of coating solids.
According to the invention, the polyester-urethane resin and/or the coating comprising the polyester-urethane resin is substantially free of epoxide. As used herein, the term "substantially epoxide-free" means that the polyester-urethane resin and/or coatings comprising the same are substantially free of epoxide, epoxide residues, ethylene oxide rings or ethylene oxide ring residues, adducts of bisphenol A, BADGE or BADGE, adducts of bisphenol F, BFDGE or BFDGE. The polyester-urethane resin and/or coating comprising the same may be substantially free of bisphenols or residues thereof, including bisphenol a, bisphenol F, BADGE, and BFDGE. The polyester-urethane resin and/or coating comprising the same may also be substantially free of polyvinyl chloride or related halide-containing vinyl polymers. By "substantially free" it is meant that the polyester and/or coating comprises 10 wt.% or less, such as 5 wt.% or less, 2 wt.% or less or 1 wt.% or less, based on the total weight of solids, of the compound in the form listed herein or other known forms. Thus, it is to be understood that the polyester-urethane resins and/or coatings comprising the same according to the present invention may comprise trace or minor amounts of these components, but are still "substantially free" of them. The present invention also contemplates the polyester-urethane resins and/or coatings comprising the same, which are completely free of any of the above listed compounds or derivatives thereof.
The coatings of the present invention can be applied to any substrate known in the art, such as automotive substrates, industrial substrates, packaging substrates, wood flooring materials and furniture, apparel, electronic devices including housings and circuit boards, glass and transparencies, and sporting equipment including golf balls, and the like. These substrates may be metallic or non-metallic, for example. The metal substrate comprises tin, steel, tin-plated steel, chromium-passivated steel, galvanized steel, aluminum and aluminum foil. Non-metallic substrates include polymers, plastics, polyesters, polyolefins, polyamides, celluloses, polystyrenes, polyacrylics, poly (ethylene naphthalate), polypropylene, polyethylene, nylons, EVOH, polylactic acid, other "green" polymer substrates, poly (ethylene terephthalate) ("PET"), polycarbonate acrylonitrile butadiene styrene ("PC/ABS"), polyamides, wood, veneer, engineered wood materials, particle board, medium density fiberboard, cement, stone, glass, paper, cardboard, textiles, and synthetic and natural leathers, and the like. The substrate may be treated in some manner, for example to provide visual and/or color effects.
The coatings of the present invention may be applied by any standard process in the art, such as electrocoating, spraying, electrostatic spraying, dipping, rolling, brushing, and the like.
The coating may be applied to a dry film thickness of 0.04 mils to 4 mils, such as 0.3 to 2 or 0.7 to 1.3 mils. It is also contemplated that the coating may be applied to a dry film thickness of 0.1 mil or greater, 0.5 mil or greater, 1.0 mil or greater, 2.0 mil or greater, 5.0 mil or greater, or even greater. The coating of the present invention may be used alone or in combination with one or more other coatings. For example, the coatings of the present invention may or may not contain colorants and may be used as primers, basecoats, and/or topcoats. For substrates coated with multiple coatings, one or more of these coatings may be a coating as described herein. The coatings of the present invention are also useful as packaging "size" coatings, size primers, spray coatings, and end-face coatings, among others.
As previously mentioned, the polyester-urethane resin of the present invention may be used in an automotive coating composition. Further, the polyester resin may be used to form a multilayer coating system, which may include two or more coating layers, at least one of which comprises a polyester-urethane resin as described herein. For example, a multi-layer coating system can include a first basecoat layer and an optional clearcoat layer. The multi-layer coating system can further include a second basecoat layer and an optional electrodeposited coating layer. The coating composition of the present invention is particularly suitable for use in compression coating processes. "compression coating process" or "compression process" is a process in which at least one curing step is eliminated from the standard automotive coating process; in other words, one or more curing steps are combined in a compression coating process such that one or more coating layers may be deposited in a "wet-on-wet" application on a previous coating layer, which may optionally be dried but not cured, with the layers being cured simultaneously. Generally, the compression method will eliminate the use and need to cure the primer-surfacer layer; in the compression method, the standard primer-surfacer layer can be replaced with the first basecoat layer. Some compression methods apply two basecoat layers, also referred to as a first basecoat layer (B1) and a second basecoat layer (B2), to a substrate. The polyester-urethane resins disclosed herein may be used in the lacquer compositions that form either or both of the first and second lacquer layers.
The optional electrodeposition coating composition of the multilayer coating system may include conventional anionic or cationic electrodepositable coating compositions, such as epoxy compound or polyurethane based coatings. Suitable electrodepositable coating compositions are described in U.S. patent nos. 4,933,056; 5,530,043, respectively; 5,760,107 and 5,820,987. If used, the cured electrodeposited layer may have a dry film thickness of up to 100 microns, such as 15-50 microns.
As noted above, when one or more basecoats are used in a multi-layer coating system, they can be deposited from the coating compositions of the present invention. Other suitable lacquer compositions that can be used in the multi-layer coating system of the present invention are discussed in us patents 8,152,982 and 8,846,156. If two or more basecoats are used, these basecoats can be the same or different. "different" may include at least two different coating compositions, at least one of which is a coating composition incorporating a branched unsaturated polyester-urethane resin according to the present invention. "different" may also include at least two different coating compositions incorporating the branched polyester-urethane resin, but in different amounts, proportions, and/or including other components or additives. After application to at least a portion of the substrate, the first lacquer composition may be dried at ambient or elevated temperature, for example by forced air drying, or thermally cured. "dried," "drying," and like terms, when used in relation to applying a coating, refer to removing at least some water and/or solvent from the coating composition at a temperature below that required to cure the coating, and include, for example, methods such as flashing or dehydrating. For example, drying may include "flash evaporation," which is typically performed by exposing the coated substrate to ambient or slightly elevated temperatures (typically 40 ℃ or less) for a brief period of time (typically 30 seconds to 20 minutes) to remove some of the solvent, but not as much as in a dehydration process; in the dehydration process, the coated substrate is exposed to a temperature (typically in the range of 40 ℃ to 121 ℃) for a period of time sufficient to remove the solvent but insufficient to cure the coated substrate, such as 1 to 10 minutes. By "ambient" drying, it is meant that at least a portion of the coating composition solvent, e.g., including water or organic solvent, can be removed without the aid of heat or energy, e.g., without oven baking, using forced air, etc.
Similarly, if used, a second basecoat layer may be deposited on at least a portion of the substrate coated with the first basecoat, and the coated substrate is again subjected to the drying step described above. If the first basecoat is only dry and not cured, both basecoat layers may be cured simultaneously. It will be appreciated that one curing step may therefore be eliminated by applying the second lacquer wet-on-wet on the uncured first lacquer, and curing both lacquers simultaneously. The dry film thickness of the first and second basecoat layers (or alternatively, a single basecoat layer, where applicable) may be up to 100 microns, but is typically from 1 to 50, such as from 5 to 30, or from 10 to 25 microns.
The multi-layer coating system may optionally include a clearcoat layer. If used, the varnish composition may comprise a branched unsaturated polyester-urethane resin of the present invention. Alternatively, the present invention may comprise the use of conventional varnish compositions. Varnish is understood to be a substantially transparent coating. Thus, the varnish may have a degree of color as long as it does not make the varnish opaque or otherwise affect the ability to see the underlying substrate to any significant degree. The clear coat may be used, for example, in combination with a pigmented base coat layer. The paint may be formulated in a manner known in the coatings art. Other suitable varnish compositions are described in U.S. patent 4,650,718; 5,814,410, respectively; and 5,891,981. The multi-layer coating system of the present invention can include, for example, an optional clearcoat layer deposited over at least a portion of the substrate coated with the one or more basecoat layers described above. The clearcoat layer can be applied over the basecoat layer and cured using any conventional means. The varnish may be applied to a dry but uncured lacquer and the layers cured simultaneously, or the lacquer may be cured before the varnish is applied. Once applied and cured, the varnish layer may have a dry film thickness of up to 100 microns, but generally ranges from 15 to 80 microns, such as 30 to 60 microns.
According to the invention, the coating can be used as a primer, such as an anti-chipping primer. Chipping-resistant primer coating compositions are known in the automotive OEM industry and are typically applied to various locations on a vehicle, such as the front door edge, the fender, the canopy and the a-pillar of the vehicle, before the primer-surfacer coating composition is applied over the entire body. In certain embodiments, the chipping primer coating composition need not be cured prior to application of one or more subsequent coatings. Instead, the shatter resistant primer coating composition may be subjected to an ambient flash step wherein it is exposed to ambient air for a period of time such that a portion of the organic solvent evaporates from the shatter resistant coating composition. Curing of the chipping primer coating composition is carried out simultaneously with (co-curing) one or more other coatings. Primers according to the present invention, including chipping resistant primers, typically contain some colorant and are typically used with one or more additional coating materials, for example, after electrocoating and before primer topcoats, pigmented basecoat layers, clearcoat layers, and the like.
It is to be understood that the coatings described herein may be single component ("1K") or multi-component compositions such as two-component ("2K") or more. A 1K composition is understood to mean a composition which, after production, during storage, etc., keeps all coating components in the same container. The 1K coating may be applied to the substrate and cured by any conventional means, such as by heat, pressurized air, and the like. The coating of the present invention may also be a multi-component coating, which is understood to maintain the various components separately prior to application. As noted above, the coatings of the present invention may be thermoplastic or thermosetting.
The present invention also relates to a method of forming a multi-layer coating system on a substrate, the method comprising: forming a first basecoat layer over at least a portion of the substrate by depositing a first basecoat composition over at least a portion of the substrate; optionally, drying or curing the first basecoat layer; optionally forming a second basecoat layer on at least a portion of the first basecoat layer by depositing a second basecoat composition, the second basecoat layer formed directly onto at least a portion of the first basecoat layer; optionally drying or curing the second lacquer; optionally forming a clearcoat layer over at least a portion of the outermost basecoat layer by depositing a clearcoat composition directly onto at least a portion of the outermost basecoat layer; and simultaneously curing any uncured coating layer, wherein at least one of the first and second lacquer compositions comprises a polyester-urethane resin of the present invention. The second lacquer composition, if used, may be the same as or different from the first lacquer composition. It will be appreciated that the first and second basecoats, if used, may be cured separately, may be cured simultaneously, in both cases prior to forming a subsequent coating, or may be cured simultaneously with the optional varnish. The method can further include the step of forming an electrodeposited coating layer by electrodepositing an electrodepositable coating composition on at least a portion of the substrate prior to the step of forming the first basecoat layer. The electrodeposited coating layer may be dried or cured prior to forming the first basecoat layer.
It has been surprisingly found that a multilayer coating system having a coating composition, such as a basecoat composition, incorporating the uncured branched polyester-urethane resin of the present invention can impart improved intercoat adhesion, chip resistance, and sag resistance properties in the coating as compared to similar multilayer coating systems using conventional polyester-urethane resin and polyurethane resin coating compositions. This is especially true if 10% to 30% of the OH remains unreacted in the polyester-urethane prepolymer. For example, such coatings may have a chip resistance less than 2 as measured with an Erichsen hammer test instrument model 508 operating at 2 bar and 25 ℃. Further, such coatings may have an intercoat adhesion performance of greater than 90%, and even greater than 95%, when subjected to a windshield adhesion test using a Sikaflex windshield adhesive (250HMV-2+) obtained from Silka Schweiz AG and cured at 100% humidity at a temperature of 40 ℃ for 10 days. In addition, the coatings of the present invention may have a sag resistance of greater than 15 μ, such as 20 μ or more. In other words, the coatings of the present invention can be applied to a dry film thickness of greater than 15 μ and then the paint sags to a tolerance limit of less than 3mm as described below.
Coil coatings having a wide range of applications in numerous industries are also within the scope of the present invention; as noted above, the coatings of the present invention are particularly well suited as coil coatings due to their unique combination of flexibility and hardness. Coil coatings also typically contain a colorant.
The coatings of the present invention are also suitable for use as packaging coatings. The use of various pretreatment and packaging coatings has been well established. Such pretreatments and/or coatings may be used in the context of metal cans, where the treatments and/or coatings are used to retard or inhibit corrosion, provide decorative coatings, provide ease of handling during production, and the like. A coating may be applied to the interior of the can to prevent the contents from contacting the metal of the container. Contact between the metal and the food or beverage can, for example, lead to corrosion of the metal container, which can then contaminate the food or beverage. This is true when the contents of the canister are acidic. The coating applied to the interior of the metal also helps prevent corrosion of the can top, which is the area between the product can filling line and the can lid; top corrosion is a significant problem for foods with high salt content. The coating may also be applied to the exterior of the metal can. Certain coatings of the present invention are particularly suitable for use with coil metal stock, such as coil metal stock for the production of can ends ("can end stock"), and end caps (end caps) and closures ("cap/closure stock"). Since coatings designed for can end stock and cover/baffle stock are typically applied prior to cutting and stamping the coil metal stock into sheets, they are typically flexible and ductile. For example, the feedstock is typically double coated. The coated metal stock is then stamped. For can ends, a tab opening score is then formed in the metal and the tab is joined to a separately made pin. The ends are then attached to the can body by an edging process. A similar process is performed on an "easy open can" can end. For easy open can ends, a score substantially around the circumference of the lid enables the lid to be easily opened and removed from the can, typically by pulling on a tab. For the cover/baffle, the cover/baffle stock is typically coated, such as by roll coating, and the cover and baffle are stamped from the stock; however, the cover/baffle may be applied after molding. Can coatings that implement relatively stringent temperature and/or pressure requirements should also be resistant to impact, corrosion, hazing, and/or blistering.
Accordingly, the present invention further relates to a package at least partially coated with any of the above-described coating compositions. In some examples, the package may be a metal can. The term "metal can" includes any type of metal can, container, or any type of receptacle or portion thereof for holding items. One example of a metal can is a food can; the term "food can" as used herein refers to a can, container or any type of receptacle or portion thereof for holding any type of food and/or beverage. The term "metal can" specifically includes food cans and also specifically "can ends" which are typically stamped from can end stock and used in conjunction with beverage packaging. The term "metal can" also includes in particular metal lids and/or closures, such as bottle caps, screw tops and lids of any size and pull-caps and the like. Metal cans can be used to hold other items as well as food and/or beverages including, but not limited to, personal care products, insecticidal sprayers, spray paint, and any other compound suitable for packaging in aerosol cans. These cans may include "two-piece cans" and "three-piece cans," as well as drawn and ironed one-piece cans; such unitary canisters are common in aerosol product applications. Packages coated according to the present invention may also include plastic bottles, plastic tubes, sheets and flexible packages such as those produced from PE, PP, PET and the like. The package may hold, for example, food, toothpaste, personal care products, and the like.
The coating may be applied to the interior and/or exterior of the package. For example, the coating may be roll coated onto metal used to produce two-piece food cans, three-piece food cans, can end stock, and/or lid/baffle stock. The present invention also contemplates applying the coating to the coil or sheet by roll coating; the coating is then radiation cured and the can end is stamped to produce the final product, the can end. It is also envisaged to apply the paint as an edge paint to the can end; the coating may be performed by roll coating. The edge coating acts to reduce friction to improve handling during continuous production and/or processing of the can. The coatings of the present invention may be applied to the cover and/or baffle; the coating includes, for example, a colored finish applied to the lid at the lid/baffle and/or post, particularly those with score joints at the lid base, pre-and/or post-formed protective varnishes. Decorative can stock can also be partially externally coated with the coatings described herein, and decorative coated can stock is used to form various metal cans.
Substrates coated according to the present invention can be coated with any of the above compositions by any means known in the art such as spraying, rolling, dipping, brushing, flow coating, and the like; when the substrate is electrically conductive, the coating may also be applied by electrocoating. Suitable application means can be determined by the person skilled in the art depending on the type of substrate to be coated and the action of the coating used. If desired, the above-described coating can be applied to a substrate in single or multiple layers by multiple stages of heating between each layer application. After the substrate is coated, the coating composition can be cured by any suitable means.
As used herein, unless otherwise specified, all numbers, such as those expressing values, ranges, amounts or percentages, are to be considered as prefixed by the word "about", even if the term does not expressly appear. Moreover, any numerical range recited herein is intended to include all sub-ranges subsumed therein. Singular encompasses plural and vice versa. For example, although "a" polyester-urethane resin, "an" unsaturated acid/anhydride/ester, "a" polyester prepolymer, "a" urethane segment, "a" polyol segment, "a" crosslinker, etc., are used herein, one or more of these components and any other component may be used. As used herein, the term "polymer" refers to oligomers as well as homopolymers and copolymers, and the prefix "poly" refers to two or more. The terms "include", "including" and the like mean including but not limited to. Where ranges have been given, ranges and/or numerical endpoints within these ranges can be incorporated within the scope of the present invention. Accordingly, the present invention is particularly directed, without limitation, to the following aspects 1-20:
1. a curable branched polyester-urethane polymer prepared by preparing:
I) free radical polymerization of an ethylenically unsaturated polyester-urethane prepolymer, the prepolymer comprising:
i. the remainder of the polyol;
the remainder of the ethylenically unsaturated polycarboxylic acid, anhydride and/or ester; and
the remainder of the isocyanate functional compound; or by
II) free radical polymerization of a hydroxy-functional ethylenically unsaturated polyester prepolymer comprising:
i. the remainder of the polyol; and
the remainder of the ethylenically unsaturated polycarboxylic acid, anhydride and/or ester;
to form a hydroxyl-functional polyester polymer,
and reacting the hydroxyl functional polyester polymer with an isocyanate functional compound.
2. The polyester-urethane polymer according to aspect 1, wherein the ethylenically unsaturated polyester-urethane prepolymer is free-radically polymerized in the presence of a second ethylenically unsaturated prepolymer, the second ethylenically unsaturated prepolymer polyester prepolymer or polyester-urethane prepolymer comprising:
i. the remainder of the polyol;
the remainder of the ethylenically unsaturated polycarboxylic acid, anhydride and/or ester; and optionally
The remainder of the isocyanate functional compound.
3. The polyester-urethane polymer according to any one of aspects 1 or 2, wherein the polyol comprises neopentyl glycol and/or wherein the ethylenically unsaturated polycarboxylic acid, anhydride and/or ester comprises maleic acid, maleic anhydride and/or an ester of maleic acid.
4. The polyester-urethane polymer according to any one of the preceding aspects 1 to 3, wherein the isocyanate functional compound comprises isophorone diisocyanate.
5. The polyester-urethane polymer according to any one of the preceding aspects 1 to 4, wherein the polyester-urethane prepolymer is reacted with a carboxylic acid, anhydride or ester and neutralized with an amine and then subjected to radical polymerization, or wherein the reaction product of a hydroxy-functional polyester polymer and an isocyanate-functional compound is reacted with a carboxylic acid, neutralized with an amine and dispersed in water.
6. The polyester-urethane polymer according to aspect 5, wherein the carboxylic acid comprises 2, 2-dimethylolpropionic acid and the amine comprises triethylamine.
7. The polyester-urethane polymer according to any one of the preceding aspects 1 to 6, wherein the radical polymerization occurs in an aqueous solution.
8. The polyester-urethane polymer according to any one of the preceding aspects 1 to 7, which has a weight average molecular weight (M)w) At least 15,000, such as at least 30,000, or in the range of 15,000 and 100,000, as determined by gel permeation chromatography using polystyrene standards for calibration.
9. The polyester-urethane polymer according to any one of the preceding aspects 1 to 8, wherein the polyester-urethane prepolymer has a weight average molecular weight (M)w) Is 2,500 or higher, as determined by gel permeation chromatography using polystyrene standards for calibration.
10. The polyester-urethane polymer according to any one of the preceding aspects 1 to 9, not comprising a residual portion of (meth) acrylate or (meth) acrylic acid.
11. The polyester-urethane polymer according to any one of the preceding aspects 1 to 10, which has a hydroxyl value of 75 to 120mg KOH/g.
12. A curable coating composition, preferably a lacquer composition, comprising:
(a) the polyester-urethane polymer according to any one of the preceding aspects 1 to 11,
(b) a curing agent having a plurality of functional groups reactive with the polyester-urethane polymer (a).
13. A method of forming a multi-layer coating on a substrate, the method comprising the steps of:
forming a first basecoat layer over at least a portion of the substrate by applying a first basecoat composition over at least a portion of the substrate;
optionally, drying or curing the first basecoat layer;
forming a second basecoat layer over at least a portion of the first basecoat layer by applying a second basecoat composition directly onto at least a portion of the first basecoat layer, the second basecoat composition being the same or different than the first basecoat composition;
optionally, drying or curing the second basecoat layer; and
curing any of the uncured coating layer(s),
wherein at least one of the first and second lacquer compositions comprises a curable coating composition according to aspect 12.
14. The method according to aspect 13, wherein the second lacquer composition is different from the first lacquer composition and/or comprises a curable coating composition according to aspect 12.
15. The method according to any one of aspects 13 or 14, further comprising forming an electrodeposited coating layer by electrodepositing an electrodepositable coating composition on at least a portion of the substrate prior to the step of forming the first basecoat layer.
16. The method according to any one of the preceding aspects 13-15, further comprising forming a clearcoat layer over at least a portion of the second basecoat layer by depositing a clearcoat composition over at least a portion of the second basecoat layer.
17. A substrate comprising at least one coating layer at least partially coated with a coating material, obtained by:
(a) applying a curable coating composition according to aspect 12 to at least a portion of a surface of a substrate, and
(b) at least partially curing the applied curable coating composition.
18. The coated substrate according to aspect 17, wherein the coating has a chip resistance of less than 2 as measured by an Erichsen hammer impact test instrument model 508 operating at 2 bar and 25 ℃.
19. A coated substrate according to any one of aspects 17 or 18, which is a substrate coated with a multi-layer coating formed according to the method of any one of aspects 13-16.
20. The coated substrate according to any one of aspects 17-19, wherein the substrate is a part of a vehicle.
Examples
The following examples are intended to illustrate the invention and should not be construed as limiting it in any way.
Preparation of unsaturated polyester prepolymer
The unsaturated polyester prepolymer was prepared from the following ingredients described below: a total of 3327.5 grams of neopentyl glycol, 3350.9 grams of adipic acid, 321.5 grams of maleic anhydride and 0.203 grams of butylstannoic acid were charged to a suitable reaction vessel equipped with a stirrer, a temperature probe and a glycol recovery unit (packed column with empty column at the top and distillation head connected to a water cooled condenser) and a nitrogen sparge. The contents of the flask were heated to 215 ℃ while the continuous removal of the water fraction was started at about 140 ℃. The temperature of the contents was maintained at 215 ℃ until about 892 grams of water were distilled off and the acid number of the reaction mixture was found to be 1.86mg KOH/g. The contents of the reactor were cooled to 160 ℃ and then diluted to 75% theoretical solids with 2040 grams of PROGLYDE DMM. The reaction product had a measured solids of 73.7%, a hydroxyl number of 72.8mg KOH/g and a weight average molecular weight of 3434, as determined against polystyrene standards.
Preparation of uncured branched polyester-urethane resin
Example 1
A total of 1316.9 grams of the unsaturated polyester prepolymer prepared above was addedAnd 187.1 grams of PROGLYDE DDM were placed in a suitable reaction vessel equipped with a stirrer temperature probe, reflux condenser, and nitrogen enclosure. The contents of the flask were mixed and heated to 45 ℃ and 231.7 grams of isophorone diisocyanate were added dropwise from the dropping funnel to the reaction contents over 30 minutes, followed by a funnel rinse of 20.4 grams of PROGLYDE DMM. After about 98 minutes, the contents of the flask were heated to 55 ℃. Isocyanate (NCO) equivalent weight was checked by titration every 30 minutes until the NCO value reached about 1655. A total of 69.7 grams of 2, 2-dimethylolpropionic acid was added to the flask followed by a rinse of 42.1 grams of trimethylamine and 10.2 grams of PROGLYDE DMM. The contents of the flask were heated to 80 ℃ until in the Fourier transform Infrared Spectroscopy (FTIR) at about 2265cm-1The isocyanate (b) disappears. A total of 19.8 grams of trimellitic anhydride was added to the flask via a powder funnel. The contents of the flask were maintained at 80 ℃ until about 1790cm in the FTIR spectrum-1The anhydride peak of (a) disappears. The milliequivalent (meq) of base was found to be 0.186. 24.0 grams of triethylamine was added to the flask to make a theoretical% total neutralization to about 80%. Triethylamine was washed with 6.1 grams PROGLYDE DMM. After stirring for about 15 minutes, 1747.8 grams of deionized water were added to the reaction contents over 30 minutes. The contents of the flask were heated to 80 ℃ over 30 minutes. Once the contents reached a temperature of 80 deg.C, 20.5 grams of the contents were added in about 1 minute
Figure BDA0001695652100000281
A mixture of 26 (available from Arkema) and 10.3 grams PROGLYDE DMM was added to the flask, followed by a 10.2 gram rinse of PROGLYDE DMM. The contents of the flask were held at 80 ℃ for 1 hour and then cooled to 45 ℃. 17.7 grams of deionized water was added to the flask at 45 ℃. After stirring for 3 minutes, the reactor contents were poured out. The final resin had a measured solids of 35.4%, a Brookfield viscosity (#1 spindle, 50rpm, 25 ℃) of about 103cp and a weight average molecular weight of 37334, measured relative to a polystyrene standard. The theoretical hydroxyl number of the polyurethane dispersion, calculated as solid resin, was 24.9mg KOH/g of sample.
Example 2
A total of 1316.9 grams of the unsaturated polyester prepolymer prepared above and 187.1 grams of PROGLYDE DDM were placed in a suitable reaction vessel equipped with a stirrer, temperature probe, reflux condenser, and nitrogen enclosure.
The contents of the flask were heated to 45 ℃ and 247.5 grams of isophorone diisocyanate were added over 30 minutes from the dropping funnel, followed by 20.4 grams of PROGLYDETMThe funnel of the DMM was rinsed. After about 70 minutes, the flask was warmed to 55 ℃. The isocyanate (NCO) equivalent weight was checked by titration every 30-60 minutes until it reached about 1574. 69.3 grams of 2, 2-dimethylolpropionic acid was then added to the flask, followed by 41.9 grams of triethylamine, and 10.1 grams of PROGLYDETMAnd (5) washing the DMM. The contents of the flask were heated to 80 ℃ until1In the FTIR spectrum at about 2265cm-1The isocyanate peak of (2) disappears. Then, 19.7 g of trimellitic anhydride was added to the flask via a powder funnel. The contents of the flask were maintained at 80 ℃ until about 1790cm in the FTIR spectrum-1The anhydride peak of (a) disappears. The milliequivalent (meq) of base was found to be 0.212. 18.6 g of triethylamine are added to bring the theoretical% total neutralization to about 80%. 6.0 g PROGLYDE was used for triethylamineTMAnd (5) washing the DMM. After stirring for about 15 minutes, 1771.8 grams of deionized water were added over 30 minutes. The contents of the flask were heated to 80 ℃ over 30 minutes. Once the contents reached a temperature of 80 deg.C, 20.4 grams of the contents were added in about 1 minute
Figure BDA0001695652100000291
26 (available from Arkema) and 10.2 grams PROGLYDETMThe mixture of DMM was added to the flask, followed by 10.2 grams of PROGLYDETMAnd (5) washing the DMM. The contents of the flask were held at 80 ℃ for 1 hour and then cooled to 45 ℃. At 45 deg.C, 17.6 grams of deionized water was added. After stirring for a few minutes the reactor contents were poured out. The final polyurethane dispersion had a measured percent solids (110 ℃/1 hour) of about 35.7%, a meq acid of 0.203, a meq base of 0.149, a pH of 7.23 and a Brookfield viscosity (#1 spindle, 50rpm, 25 ℃) of about 423 cp. The theoretical hydroxyl value of the polyurethane dispersion, calculated as solid resin, was 18.6 mgKOH/gram of sample.
Examples3
A total of 1316.9 grams of the unsaturated polyester prepolymer prepared above and 187.1 grams of PROGLYDE DDM were placed in a suitable reaction vessel equipped with a stirrer, temperature probe, reflux condenser, and nitrogen enclosure. The contents of the flask were heated to 45 ℃ and 247.5 grams of isophorone diisocyanate were added from the dropping funnel over 30 minutes, followed by 20.4 grams of PROGLYDETMThe funnel of the DMM was rinsed. The flask was then warmed to 55 ℃. The isocyanate (NCO) equivalent weight was checked by titration every 30 minutes until it reached about 1505. 69.5 grams of 2, 2-dimethylolpropionic acid was then added to the flask, followed by 42.0 grams of triethylamine and 10.1 grams of PROGLYDETMAnd (5) washing the DMM. The contents of the flask were heated to 80 ℃ until they were in the FTIR spectrum at about 2265cm-1The isocyanate peak of (2) disappears. Then, 19.8 g of trimellitic anhydride was added to the flask via a powder funnel. The contents of the flask were maintained at 80 ℃ until about 1790cm in the FTIR spectrum-1The anhydride peak of (a) disappears. The milliequivalent (meq) of base was found to be 0.207. 19.8 g of triethylamine were added to total neutralize to about 80% of theory. 6.1 g PROGLYDE was used for triethylamineTMAnd (5) washing the DMM. After stirring for about 15 minutes, 1806.3 grams of deionized water were added over 30 minutes. The contents of the flask were heated to 80 ℃ over 30 minutes. Once the contents reached a temperature of 80 deg.C, 20.5 grams of the contents were added in about 1 minute
Figure BDA0001695652100000301
26 (available from Arkema) and 10.2 grams PROGLYDETMThe mixture of DMM was added to the flask, followed by 10.2 grams of PROGLYDETMAnd (5) washing the DMM. The contents of the flask were held at 80 ℃ for about 1 hour. After half of the 1 hour hold, 538 grams of deionized water was slowly added to the flask. After the 1 hour hold was complete, the contents of the flask were cooled to 45 ℃. At 45 deg.C, 17.6 grams of deionized water was added. After stirring for a few minutes, the reactor contents were poured out. The final polyurethane dispersion measured a percent solids (110 ℃/1 hour) of about 31.3%, a meq acid of 0.174, a meq base of 0.127, a pH of 7.26 and a Brookfield viscosity (#1 spindle, 50 rp) ofm, 25 ℃) was about 306 cp. The theoretical hydroxyl value of the polyurethane dispersion, calculated as solid resin, was 12.4 mgKOH/gram of sample.
The coating composition comprises an uncured branched polyester-urethane resin
Table 1 lists the ingredients used to prepare five stain-based paint samples (samples 3, 4 and 5) using an uncured branched polyester-urethane resin of the invention (the polyester-urethane resin of example 1) and two comparative stain-based paint samples (samples 1 and 2):
comparative sample 1 used neither a commercially available polyurethane resin nor the polyester-urethane resin of the present invention. Comparative sample 2 used a commercially available polyurethane resin. Samples 3, 4 and 5 used the polyester-urethane resin of the present invention.
TABLE 1
Figure BDA0001695652100000311
1Polyester-urethane resin of example 1:
2polyurethane resin Witco Bond 272, available from Chemtura Corp.
3The polyurethane acrylic latex polymer described in example IIA of us patent 5,972,809.
4An acrylic dispersion made from: 30.0 wt.% styrene, 35.0 wt.% n-butyl acrylate, 18.0 wt.% n-butyl methacrylate and 8.5 wt.% 2-hydroxyethyl acrylate and 8.5 wt.% acrylic acid, in a solvent mixture of 84.5 wt.% deionized water/15.5 wt.% butyl carbitol 26.1 wt.% solids, 54% neutralized with dimethylethanolamine.
5The polyester resin polymer described in example 2 of U.S. patent 5,468,802.
6Dimethylethanolamine (50% aqueous solution)
7A phosphated epoxy resin prepared by: epon 828, of bisphenol APolyglycidyl ethers available from Shell Chemical Co; with phosphoric acid at 83: 18 weight ratio.
8An additive, available from Byk Chemie.
9Polyether polyols, available from Bayer Material Science.
10Melamine curing agent, commercially available from INEOS Melamine.
11，12Solvent, available from Dow Co.
13Solvent, available from Shell Chemical Co.
14Surfactants, available from Air Products&Chemicals。
15White toning paste with 50% TiO2And a solids content of 62%.
16Red toning paste with 34% ferrous oxide and 46% solids content.
17A purple tinting paste with 12% Hostaperm Violet RL specialty commercially available from Clariant Pigments and a solids content of 25%.
18Black toning paste with 5% Monarch 120 and 24% solids content.
19A 9% Aerosil R812 dispersion, commercially available from Evonik Degussa, in a 21% acrylic polymer blend and at a solids content of 31%.
The basecoats were sprayed onto 12 inch by 20 inch steel panels coated with cured ELECTROCOAT (ED 6060CZ) and primer (A-F106820-4P5) available from PPG Industries, Italy, using a Labpainter machine manufactured by LacTec Gmbh, in an environment controlled at 70-75F (21-24℃) and 50-60% relative humidity. For the shatter resistance and adhesion tests, the lacquer was sprayed onto the panel and flashed off at ambient temperature for a period of 5 minutes and then baked at 80 ℃ for a period of 10 minutes. A varnish (A-F105359-4C0) available from PPG Industries, Italy, was sprayed onto the base paint and flashed off at ambient temperature for a period of 10 minutes. The entire multilayer system was baked at 140 ℃ for a period of 30 minutes. The dry film thicknesses of the basecoats and clearcoats were 0.7-0.8 mils and 1.6-2.3 mils, respectively.
For sag resistance, 12 inch by 20 inch steel panels coated with cured ELECTROCOAT (ED 6060CZ) and primer (A-F106820-4P5) available from PPG Industries, Italy were sprayed with the paint base compositions of samples 1-5. The holes (each 10 mm diameter) were perforated equidistantly along the length of each test steel plate. To apply each of the lacquer compositions, the test panel was positioned vertically with the holes running from left to right. Each of the base paint compositions of samples 1-5 was sprayed onto a test panel using an automated spray equipment under controlled conditions of 70-75F (21-24℃) and 50-60% relative humidity to produce a wedge-shaped film thickness (i.e., increasing film thickness from left to right on the test panel) of the composition in each spray, also referred to as a "wedge-shaped panel". Each coated test panel was then "flashed" at ambient temperature for a period of 5 minutes and then baked at 80 ℃ for a period of 10 minutes. Clear coats available from PPG Industries, Italy (A-F105359-4C0) were sprayed onto the basecoats and flashed off at ambient temperature for a period of 10 minutes. The entire multilayer system was baked at 140 ℃ for a period of 30 minutes. The test panels were hung vertically until fully cured. Sag resistance is measured by recording the "sag" length (millimeters), i.e., the length of coating that runs out of the bottom of the hole, at a given dry film thickness. For the purposes of this invention, acceptable coating sag is measured once coating sag from the bottom of the well reaches a tolerance limit below 3mm at a given dry film thickness. In the present invention, the dry film thickness of the basecoat is 0.2 to 1.4 mils, and the dry film thickness of the clearcoat is 1.6 to 2.3 mils (measured from left to right on a steel panel). The sag resistance test results are given in table 2 below, where higher values indicate better sag resistance.
Table 2 provides a summary of the performance and physical properties obtained from each of the above samples.
TABLE 2
Sample (I) Paint adhesion test11 Adhesion of windshield12 Resistance to cracking13 Sag resistance14
1 20％ 20％ 2.5 25μ
2 40％ 50％ 2 15μ
3 100％ 100％ 1.5 20μ
4 100％ 100％ 1.5 20μ
5 80％ 100％ 1.5 20μ
11Paint adhesion test A Walter cleaning System steam jet test apparatus (PMEG-2506) model LTA1-H-A-T80-LP-PA with 1/4HP nozzles was performed as follows: test panels were prepared as above for each of samples 1-5. The coated test panels were scribed in a criss-cross pattern. A high pressure steam jet was directed at the scribed test panel at a temperature of 60c, a pressure of 70 bar, a distance of 10cm from the nozzle to the test panel, an angle of 90 deg. relative to the test panel and a time of 1 minute to pressurise the coating. Paint adhesion was visually detected and measured by the popular (VW) test method PV 1503B. Higher percentage values indicate better paint adhesion.
12Windshield adhesion testing was performed and measured as follows: the windshield adhesive beads were applied to the varnish surface within 1-4 hours after the final bake (30 minutes at 140 ℃). Sikaflex windshield adhesive (250HMV-2+) was used, available from Silka Schweiz AG. Adhesive beads of approximately 20mm x 200mm x 50mm were placed on the cured colored and transparent substrate. The adhesive was cured at 100% humidity at a temperature of 40 ℃ for 10 days. After a curing time of 10 days, the adhesive bead was cut with a razor blade while peeling off the adhesive edge at an angle of 180 °. Each system was cut 10 times. Any delamination of the multilayer coating was visually detected and measured. The result of 90-100% of the coating remaining adhered to the substrate is considered "acceptable" or "pass through" in the automotive industry. When 0% to 10% of the coating delaminated from the substrate, it was considered "failed".
13ERICHSEN GMBH for shatter resistance test&Hammer strike test instrument model 508, made by CO KG, was performed as follows: each coated test panel was impacted twice with 500 grams of a 4-5mm size break steel shot and at a pressure of 200 Kpa. The hammer strike test determines the ability of the multilayer coating system to withstand impacts resulting from small objects striking the test substrate at high speeds, similar to a stone striking a high speed running automobile. Visual assessment from DIN EN ISO 20567-1The score is used to score the board. The score ranged from 0.5 to 5, with lower values indicating better chipping resistance.
14Sag resistance was measured by visual inspection and the length of sag (millimeters) was recorded, with higher values indicating better sag resistance.
The results in Table 2 above show that a lacquer having sufficient intercoat adhesion, chip resistance and sag resistance properties can be prepared according to the invention.

Claims (29)

1. An uncured, branched polyester-urethane resin prepared by free radical polymerization of the double bonds of an unsaturated polyester-urethane prepolymer comprising:
a) a polyol segment;
b) unsaturated polycarboxylic acids and/or anhydrides and/or esters thereof; and
c) a urethane segment formed by the reaction of an isocyanate comprising a cycloaliphatic polyisocyanate or an isocyanate prepolymer prepared with a polyol with at least one hydroxyl group from the polyol segment;
wherein the amount of urethane segments present in the final polyester-urethane resin is from 10 to 25 weight percent based on the total weight of the polyester-urethane prepolymer.
2. The uncured, branched polyester-urethane resin of claim 1 wherein the polyol is a polymer polyol.
3. The uncured, branched polyester-urethane resin of claim 1 wherein the polyol segment comprises neopentyl glycol and the unsaturated polycarboxylic acid, anhydride and/or ester segment comprises maleic acid, maleic anhydride and/or an ester of maleic acid.
4. The uncured, branched polyester-urethane resin of claim 1 wherein the polyester-urethane prepolymer is reacted with a carboxylic acid, anhydride or ester and neutralized with an amine, followed by free radical polymerization.
5. The uncured, branched polyester-urethane resin of claim 4 wherein the carboxylic acid comprises 2, 2-dimethylolpropionic acid and the amine comprises triethylamine.
6. The uncured, branched polyester-urethane resin of claim 1 wherein the isocyanate comprises isophorone diisocyanate.
7. The uncured, branched polyester-urethane resin of claim 1 wherein the free radical polymerization occurs in an aqueous solution.
8. The uncured, branched polyester-urethane resin of claim 1 wherein the Mw of the polyester-urethane resin is 15,000-100,000 as determined by gel permeation chromatography using polystyrene standards for calibration.
9. The uncured, branched polyester-urethane resin of claim 1 wherein the polyester-urethane resin has a Mw of 30,000 or more as determined by gel permeation chromatography using polystyrene standards for calibration.
10. The uncured, branched polyester-urethane resin of claim 1 wherein the polyester-urethane prepolymer has a Mw of 2,500 or more as determined by gel permeation chromatography using polystyrene standards for calibration.
11. The uncured, branched polyester-urethane resin of claim 1 wherein the polyester-urethane resin does not comprise (meth) acrylates or residues thereof.
12. The uncured, branched polyester-urethane resin of claim 1 wherein the polyester-urethane resin has a hydroxyl number of 75 to 120mg KOH/gram as measured by ASTM method D4274.
13. A coating composition comprising the uncured branched polyester-urethane resin of claim 1 and a crosslinker therefor.
14. The coating composition of claim 13 having a chip resistance of less than 2 as measured by Erichsen hammer impact tester model 508 operating at 2 bar and 25 ℃.
15. The coating composition of claim 13, wherein the polyol segment comprises neopentyl glycol and the unsaturated polycarboxylic acid, anhydride and/or ester segment comprises maleic acid, maleic anhydride and/or an ester of maleic acid.
16. The coating composition of claim 13, wherein the coating composition is a lacquer.
17. A substrate at least partially coated with the coating composition of claim 13.
18. The substrate of claim 17, wherein the substrate is part of a vehicle.
19. A method of forming a multi-layer coating system on a substrate, the method comprising:
forming a first basecoat layer over at least a portion of the substrate by depositing a first basecoat composition over at least a portion of the substrate;
optionally, drying or curing the first basecoat layer;
forming a second basecoat layer over at least a portion of the first basecoat layer by depositing a second basecoat composition directly over at least a portion of the first basecoat layer, the second basecoat composition being the same or different than the first basecoat composition;
optionally, drying or curing the second basecoat layer; and
curing any of the uncured coating layer(s),
wherein at least one of the first and second lacquer compositions comprises the coating composition of claim 13.
20. The method of claim 19, further comprising forming a varnish composition on at least a portion of the second basecoat layer by depositing a varnish composition over at least a portion of the second basecoat layer.
21. The method of claim 19, further comprising forming an electrodeposited coating layer by electrodepositing an electrodepositable coating composition on at least a portion of the substrate prior to the step of forming the first basecoat layer.
22. The method of claim 19, wherein the second lacquer composition is different from the first lacquer composition.
23. The method of claim 19, wherein the second lacquer composition comprises the coating composition of claim 13.
24. An uncured branched polyester-urethane resin prepared by:
a) free radical polymerizing the double bonds of at least one unsaturated polyester prepolymer having hydroxyl functionality to form a polyester polymer, and
b) reacting the hydroxyl functional groups in the polyester polymer of step a) with an isocyanate comprising a cycloaliphatic polyisocyanate or an isocyanate prepolymer prepared with a polyol, wherein the ratio of isocyanate functional groups (NCO) to hydroxyl groups (OH) is 1: 2-1: 1.5;
wherein the polyester prepolymer comprises:
i) a polyol segment; and
ii) unsaturated polycarboxylic acids and/or anhydrides and/or ester segments.
25. The uncured, branched polyester-urethane resin of claim 24 wherein the polyol is a polymer polyol.
26. The uncured, branched polyester-urethane resin of claim 24 wherein the reaction product of step b) is reacted with a carboxylic acid and neutralized with an amine and dispersed in water.
27. The uncured, branched polyester-urethane resin of claim 24 wherein the isocyanate comprises isophorone diisocyanate.
28. An uncured, branched polyester-urethane resin prepared by free radical polymerization of double bonds of a first unsaturated polyester prepolymer and double bonds of a second unsaturated polyester prepolymer, wherein each prepolymer independently comprises:
a) a polyol segment; and
b) unsaturated polycarboxylic acids and/or anhydrides and/or ester segments; and wherein at least one of the unsaturated polyester prepolymers contains a urethane segment formed by the reaction of an isocyanate comprising a cycloaliphatic polyisocyanate or an isocyanate prepolymer prepared with a polyol with at least one hydroxyl group from the polyol segment, and wherein the prepolymers are the same or different;
wherein the amount of urethane segments present in the final polyester-urethane resin is from 10 to 25 weight percent based on the total weight of the polyester-urethane prepolymer.
29. The uncured, branched polyester-urethane resin of claim 28 wherein the polyol is a polymer polyol.
CN201680073282.5A 2015-12-14 2016-12-13 Branched polyester-urethane resins and coatings comprising the same Active CN108473655B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US14/967,763 US10035872B2 (en) 2010-04-01 2015-12-14 Branched polyester-urethane resins and coatings comprising the same
US14/967,763 2015-12-14
PCT/US2016/066303 WO2017106152A2 (en) 2015-12-14 2016-12-13 Branched polyester-urethane resins and coatings comprising the same

Publications (2)

Publication Number Publication Date
CN108473655A CN108473655A (en) 2018-08-31
CN108473655B true CN108473655B (en) 2021-08-03

Family

ID=58745340

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201680073282.5A Active CN108473655B (en) 2015-12-14 2016-12-13 Branched polyester-urethane resins and coatings comprising the same

Country Status (7)

Country Link
EP (1) EP3390484A2 (en)
KR (1) KR102080423B1 (en)
CN (1) CN108473655B (en)
CA (1) CA3008414C (en)
MX (1) MX2018007177A (en)
RU (1) RU2018125548A (en)
WO (1) WO2017106152A2 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115717018A (en) * 2022-12-05 2023-02-28 德清县金秋塑粉有限公司 Special anticorrosive powder coating for suspension spring of automobile shock absorber

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104321395A (en) * 2012-04-03 2015-01-28 关西涂料株式会社 Aqueous paint composition and method for forming coating
WO2015153844A1 (en) * 2014-04-04 2015-10-08 Ppg Industries Ohio, Inc. Branched polyester polymers and soft touch coatings comprising the same

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4650718A (en) 1985-08-19 1987-03-17 Ppg Industries, Inc. Color plus clear coatings employing polyepoxides and polyacid curing agents
US4933056A (en) 1988-09-26 1990-06-12 Ppg Industries, Inc. Cationic electrodepositable compositions through the use of sulfamic acid and derivatives thereof
TW242644B (en) 1992-10-30 1995-03-11 Ppg Industries Inc
DE4317981A1 (en) 1993-05-28 1994-12-01 Ranco Inc Gas-air ratio control device for a temperature control loop for gas appliances
US5530043A (en) 1994-05-25 1996-06-25 Ppg Industries, Inc. Low volatile organic content pigment grind composition
US5582704A (en) 1994-11-04 1996-12-10 Ppg Industries, Inc. Cationic resin and capped polyisocyanate curing agent suitable for use in electrodeposition
DE69625900T2 (en) 1995-05-01 2003-09-18 Ppg Ind Ohio Inc CURABLE COMPOSITIONS FOR COMPOSITE LAYERS AND METHODS FOR IMPROVING SCRATCH AND ABRASION RESISTANCE
US5820987A (en) 1996-08-21 1998-10-13 Ppg Industries, Inc. Cationic electrocoating compositions, method of making, and use
EP1054931A1 (en) 1998-02-18 2000-11-29 PPG Industries Ohio, Inc. Low temperature cure waterborne coating compositions having improved appearance and humidity resistance and methods for coating substrates
ES2234190T3 (en) * 1998-08-17 2005-06-16 Bayer Materialscience Ag WATER COATING AGENT, ITS MANUFACTURE AND USE FOR OVEN DRYING PAINTS.
US6875800B2 (en) 2001-06-18 2005-04-05 Ppg Industries Ohio, Inc. Use of nanoparticulate organic pigments in paints and coatings
US6894086B2 (en) 2001-12-27 2005-05-17 Ppg Industries Ohio, Inc. Color effect compositions
WO2003068418A2 (en) 2002-02-13 2003-08-21 Ppg Industries Ohio, Inc. Coating line and process for forming a multilayer composite coating on a substrate
US7438972B2 (en) 2004-06-24 2008-10-21 Ppg Industries Ohio, Inc. Nanoparticle coatings for flexible and/or drawable substrates
FR2903412B1 (en) * 2006-07-07 2012-10-05 Cray Valley Sa URETHANE PRE-POLYMER - UNSATURATED POLYESTER AND APPLICATIONS THEREOF
US20110021694A1 (en) * 2009-07-23 2011-01-27 E.I. Du Pont De Nemours And Company Polyesterurethane for coating compositions
US8846156B2 (en) 2013-02-28 2014-09-30 Ppg Industries Ohio, Inc. Methods and compositions for coating substrates

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104321395A (en) * 2012-04-03 2015-01-28 关西涂料株式会社 Aqueous paint composition and method for forming coating
WO2015153844A1 (en) * 2014-04-04 2015-10-08 Ppg Industries Ohio, Inc. Branched polyester polymers and soft touch coatings comprising the same

Also Published As

Publication number Publication date
KR20180093032A (en) 2018-08-20
MX2018007177A (en) 2018-08-01
RU2018125548A (en) 2020-01-16
CA3008414A1 (en) 2017-06-22
WO2017106152A3 (en) 2017-09-14
CN108473655A (en) 2018-08-31
KR102080423B1 (en) 2020-02-21
RU2018125548A3 (en) 2020-01-16
EP3390484A2 (en) 2018-10-24
CA3008414C (en) 2021-05-18
WO2017106152A2 (en) 2017-06-22

Similar Documents

Publication Publication Date Title
US20220073783A1 (en) Hydroxy functional alkyl polyurea crosslinkers
US10273381B2 (en) Branched polyester polymers and coatings comprising the same
KR101460427B1 (en) High functionality polyesters and coatings comprising the same
US9115241B2 (en) Branched polyester polymers and soft touch coatings comprising the same
US10392467B2 (en) Coatings comprising branched polyester-urethane resins
JP2019073738A (en) Branched polyester polymers and soft touch coatings comprising the same
CN108473655B (en) Branched polyester-urethane resins and coatings comprising the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant