CN111886271A - Aqueous curable compositions comprising dispersed uretdione prepolymers, reactants, and azoles - Google Patents

Aqueous curable compositions comprising dispersed uretdione prepolymers, reactants, and azoles Download PDF

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Publication number
CN111886271A
CN111886271A CN201980021447.8A CN201980021447A CN111886271A CN 111886271 A CN111886271 A CN 111886271A CN 201980021447 A CN201980021447 A CN 201980021447A CN 111886271 A CN111886271 A CN 111886271A
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CN
China
Prior art keywords
curable composition
uretdione
aqueous curable
compound
polyols
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.)
Pending
Application number
CN201980021447.8A
Other languages
Chinese (zh)
Inventor
A·埃金
S·德尔
S·博伊克
H-J·拉斯
D·格雷茨塔-弗兰茨
N·尤瓦
R-G·博恩
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.)
Covestro Deutschland AG
Covestro LLC
Original Assignee
Covestro Deutschland AG
Covestro LLC
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 US15/933,470 external-priority patent/US11292864B2/en
Priority claimed from US15/933,500 external-priority patent/US10696775B2/en
Priority claimed from EP18163621.8A external-priority patent/EP3543270A1/en
Priority claimed from US15/933,527 external-priority patent/US20190292296A1/en
Priority claimed from US15/933,553 external-priority patent/US10633477B2/en
Priority claimed from EP18163625.9A external-priority patent/EP3543271A1/en
Priority claimed from US15/933,487 external-priority patent/US20190292305A1/en
Priority claimed from US15/933,495 external-priority patent/US11312881B2/en
Priority claimed from US15/933,507 external-priority patent/US20190292294A1/en
Priority claimed from US15/933,570 external-priority patent/US10731051B2/en
Priority claimed from US15/933,475 external-priority patent/US11008416B2/en
Priority claimed from EP18163620.0A external-priority patent/EP3543269A1/en
Priority claimed from US15/933,511 external-priority patent/US11440988B2/en
Priority claimed from EP18181876.6A external-priority patent/EP3590987A1/en
Priority claimed from EP18181877.4A external-priority patent/EP3590988A1/en
Application filed by Covestro Deutschland AG, Covestro LLC filed Critical Covestro Deutschland AG
Publication of CN111886271A publication Critical patent/CN111886271A/en
Pending legal-status Critical Current

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    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione groups
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    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
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    • C08G18/2036—Heterocyclic amines; Salts thereof containing one heterocyclic ring having at least three nitrogen atoms in the ring
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    • C08G18/3225—Polyamines
    • C08G18/325—Polyamines containing secondary or tertiary amino groups
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    • C08G2190/00—Compositions for sealing or packing joints

Abstract

The present invention relates to aqueous curable compositions comprising or consisting of A) at least one uretdione prepolymer comprising at least one uretdione group and obtainable by reacting A1) at least one uretdione polyisocyanate having an isocyanate functionality of at least 2.0, whereby the uretdione polyisocyanate is obtained from at least one aliphatic polyisocyanate, with A2) at least one compound comprising at least one Zerewitinoff-active group, and A3) at least one reactant comprising at least one Zerewitinoff-active group and being different from A2 or being H22O, preferably in the presence of at least one catalyst, to obtain a uretdione prepolymer; wherein the prepolymer has an acid number of at most 4 mg KOH/g, preferably determined in the form of a 37% by weight aqueous dispersion according to DIN EN ISO2114: 2002-06; B) optionally, at least one compound comprising at least one Zerewitinoff-active group; and C) at least one azole compound.

Description

Aqueous curable compositions comprising dispersed uretdione prepolymers, reactants, and azoles
Technical Field
The present invention relates to aqueous curable compositions that require low curing temperatures and can provide a coating on a substrate after curing. The invention also relates to a method for curing the aqueous curable composition of the invention and to the use of said composition for coatings, adhesives and/or sealants.
Background
It is known that polyaddition compounds containing uretdione groups act as crosslinkers for the preparation of polyurethane-based coatings. The crosslinking principle utilized in these crosslinkers is the thermal cleavage of the uretdione structure back to free isocyanate groups and its subsequent reaction with the hydroxy-functional binder. The thermal cracking requires a temperature of at least about 130 ℃.
Laas et al (see US 2004/0059082 a1) provide polyaddition compounds containing uretdione groups, which are obtainable by reacting uretdione polyisocyanates formed from diisocyanates having only secondary-and/or tertiary-linked isocyanate groups, which have a molar fraction of isocyanurate structures of not more than 10%, based on the sum of uretdione groups and isocyanurate groups, with compounds which are reactive toward isocyanates. The uretdione polyisocyanates are prepared from diisocyanates in which the formation of uretdione groups is promoted by an oligomerization catalyst containing 1,2, 3-or 1,2, 4-triazole (triazole) structures in the anion. The curing of powder coatings prepared from the polyaddition compounds described by Laas et al also takes place at elevated temperatures.
Mazanek et al (see US 2007/0032594) provide self-crosslinking polyurethane dispersions wherein the dispersed polyurethane contains uretdione groups.
Shaffer et al (see WO 2011/115669A 2) have succeeded in developing uretdione-based curing compositions that can be cured at low temperatures of 20 ℃ to 70 ℃. The temperature is reduced by incorporating an amine-derived catalyst into the curing composition. It has been found that if Shaffer's curing composition is applied as a solution or dispersion in a solvent, the solvent used should be inert. Shaffer et al recommend selected organic solvents, i.e., solvents suitable for use in the low temperature curing process.
It is known that uretdione groups and isocyanate moieties are susceptible to hydrolysis.
It is an object of the present invention to provide aqueous curable compositions that cure faster and/or at low temperatures. Coatings based on the aqueous curable compositions should have excellent mechanical and optical properties. The coating should be resistant to solvents, especially water. The coating can be applied on different kinds of substrates, such as textiles, plastics, glass, metal, wood, etc. The curable composition of the present invention may also serve as the base composition for the adhesive. The resulting coating is preferably transparent.
Disclosure of Invention
The present invention relates to an aqueous curable composition comprising or consisting of
A) At least one uretdione prepolymer comprising at least one uretdione group and being passable through
A1) At least one uretdione polyisocyanate having an isocyanate functionality of at least 2.0, whereby the uretdione polyisocyanate is obtained from at least one aliphatic polyisocyanate,
and
A2) at least one compound comprising at least one Zerewitinoff-active group,
and
A3) at least one reactant comprising at least oneA Zerewitinoff-active group and is different from A2 or is H2O，
Preferably in the presence of at least one catalyst, to obtain a uretdione prepolymer;
wherein the prepolymer has an acid number of at most 4 mg KOH/g, preferably determined in the form of a 37% by weight aqueous dispersion according to DIN EN ISO2114: 2002-06; and
B) optionally, at least one compound comprising at least one Zerewitinoff-active group;
and
C) at least one azole-compound (azole-compound). The invention also relates to a process for curing the composition of the invention on a substrate and to the cured articles obtained by this process. The invention also relates to the use of the composition according to the invention for coatings, adhesives and/or sealants.
Detailed Description
For the purposes of the following detailed description, it is to be understood that each numeral, except in any operating examples or where otherwise indicated, in all numbers expressing, for example, quantities of ingredients used in the specification and claims, includes "about" each numeral. For example, if the number 10 is described, then "10" and "about 10" are included.
In the present invention, any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, i.e., having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.
In the present invention, a "monomer" is a low molecular weight compound containing a functional moiety, wherein the monomer serves as a building block (building block) of a polymer and has a specified molecular weight.
In the present invention, the term "polymer" refers to a compound formed by linking several monomers of the same or different kind (i.e., more than two monomers) together via covalent bonding during a chemical reaction, wherein the resulting polymers may differ in their degree of polymerization, molecular weight distribution and chain length, respectively. Thus, the polymer according to the present invention is a compound comprising at least one repeating unit in its molecular structure, which repeating unit is combined in the polymer structure during the synthesis of the polymer by repeatedly linking monomers together via covalent bonds to form said polymer structure. The number average molecular weight is preferably at least 250 g/mol, more preferably at least 1,000 g/mol.
The term "polymer" includes homopolymers, copolymers, block copolymers and oligomers.
In the present invention, the "prepolymer" is a polymer having a reactive group. Similar to the definition of the term "polymer", the molecular structure of a prepolymer is formed by repeating the linking together of more than two monomers of the same or different species. The prepolymer may participate in the subsequent formation of a polymer having a higher molecular weight than the prepolymer. The term "prepolymer" encompasses a polymer of repeating units capable of undergoing a chemical reaction via at least one reactive group thereof to form a (preferably crosslinked) polymer. The term "prepolymer" thus also covers self-crosslinking polymers having at least two different kinds of reactive groups, wherein said groups are capable of chemically reacting with themselves, thereby enabling crosslinking of the prepolymer molecules.
According to the invention, the average molecular weight is defined as the number average molecular weight Mn, if not otherwise specified. As molecular weight of the polymer, the number average molecular weight Mn is used. Mn was determined by gel permeation chromatography (GPC at 23 ℃) in tetrahydrofuran as solvent. Measurements were carried out as described in DIN 55672-1 (the latest version of the invention used on the filing date (or priority date, if applicable): "Gelpermeationschrodigraphics, Tail 1-Tetrahydrofuranals Elutionsistel" (SECURITY GPC-System from PSS Polymer Service, flow 1.0 ml/min; column: 2 XPSS SDV Linear M, 8X 300 mm, 5 μ M; RID-detector). Polystyrene probes of known molecular weight were used for calibration. The calculation of the number average molecular weight was performed by software. The baseline values and evaluation thresholds were determined according to DIN 55672 Teil 1 cited above.
The term "low molecular weight" is defined to encompass molecular weights of up to 800 g/mol.
The term "macromolecule" is defined to encompass molecular weights above 800 g/mol.
An "organic compound" contains at least one moiety that comprises a carbon-hydrogen covalent bond.
According to the present application, the term "aliphatic" is defined as a saturated or unsaturated non-aromatic hydrocarbon radical.
According to the present application, the term "araliphatic" is defined as a hydrocarbon moiety consisting of non-aromatic as well as saturated or unsaturated hydrocarbon groups directly bonded to an aromatic moiety.
According to the present application, the term "alicyclic" or "cycloaliphatic" is an optionally substituted, carbocyclic or heterocyclic compound or moiety which is non-aromatic (e.g. cycloalkane, cycloalkene or oxa-, thia-, aza-or thiazacycloalkane). Particular examples are cyclohexyl, cyclopentyl and their N-or O-heterocyclic derivatives, such as pyrimidine, pyrazine, tetrahydropyran or tetrahydrofuran.
If a group or compound is disclosed as being "optionally substituted" or "substituted", suitable substituents are-F, -Cl, -I, -Br, -OH, -OCH3、-OCH2CH3-O-isopropyl group
or-O-n-propyl, -OCF3、-CF3、-S-C1-6-alkyl groups and/or linear or branched, aliphatic and/or cycloaliphatic structural units having from 1 to 12 carbon atoms (optionally linked by heteroatoms), respectively, acting as substitutes for carbon-bonded hydrogen atoms of the molecule. Preferred substituents are halogen (especially-F, -Cl), C1-6-alkoxy (especially methoxy and ethoxy), hydroxy, trifluoromethyl and trifluoromethoxy, respectively, serving as a substitute for a carbon-bonded hydrogen atom of the molecule.
In the formulae illustrating the structure of a chemical moiety, the covalent bond of the formula labeled with x refers to the covalent bond linking the illustrated moiety to the remaining more complex molecular structure.
The term "transparent" preferably means that the coating (having a thickness of 45 μm) is capable of transmitting visible rays, so that objects located outside or behind can be clearly seen. The clearcoats according to the invention exhibit haze values <20 (haze measuring instrument: DINEN ISO 2813 (DIN version of the latest version used on the filing date (or priority date, if applicable) of the present invention).
The invention relates in particular to:
1. an aqueous curable composition comprising or consisting of
A) At least one uretdione prepolymer comprising at least one uretdione group and being passable through
A1) At least one uretdione polyisocyanate having an isocyanate functionality of at least 2.0, whereby the uretdione polyisocyanate is obtained from at least one aliphatic polyisocyanate,
and
A2) at least one compound comprising at least one Zerewitinoff-active group,
and
A3) at least one reactant comprising at least one Zerewitinoff-active group and being different from A2 or being H2O，
Preferably in the presence of at least one catalyst, to obtain a uretdione prepolymer;
wherein the prepolymer has an acid number of at most 4 mg KOH/g, preferably determined in the form of a 37% by weight aqueous dispersion according to DIN EN ISO2114: 2002-06; and
B) optionally, at least one compound comprising at least one Zerewitinoff-active group; and
C) at least one azole-compound.
2. The aqueous curable composition according to aspect 1, characterized in that
In a first step, the at least one uretdione polyisocyanate a1 is reacted with the at least one compound a2, preferably in the presence of a catalyst, wherein the intermediate product obtained after the first step preferably has an isocyanate content of 0.5 to 10 wt.%, preferably 1 to 6 wt.%, more preferably 2 to 4 wt.%, measured according to DIN EN ISO 11909: 2007-05;
and reacting the polymer obtained in the first step with the at least one reactant a3 in a second step.
3. The aqueous curable composition according to aspect 1, characterized in that
The components A1 to A3 are reacted in a one-step process, preferably in the presence of a catalyst.
4. The aqueous curable composition according to aspect 1, characterized in that
In a first step, the at least one uretdione polyisocyanate a1 is reacted with the at least one reactant A3, and in a second step, the polymer obtained in the first step is reacted with the at least one compound a2 in a second step, preferably in the presence of a catalyst.
5. The aqueous curable composition according to any of the above aspects, characterized in that the uretdione prepolymer is a non-ionic prepolymer.
6. The aqueous curable composition according to any of the above aspects, characterized in that the uretdione prepolymer exhibits a zeta potential of at least-20 mV.
7. The aqueous curable composition according to any of the above aspects, characterized in that the uretdione prepolymer a comprises at least one x-O- (CH)2CH2O)n-R moiety, wherein R is a hydrogen atom or (C)1-C4) -alkyl and n is a number from 3 to 100.
8. The aqueous curable composition according to any of the above aspects, characterized in that the uretdione polyisocyanate a1 is obtained from at least one cycloaliphatic polyisocyanate.
9. The aqueous curable composition according to any of the above aspects, characterized in that the uretdione polyisocyanate a1 is obtained from isophorone diisocyanate (IPDI), 1, 6-hexamethylene diisocyanate or a mixture thereof.
10. The aqueous curable composition according to any of the above aspects, characterized in that the uretdione polyisocyanate a1 is prepared from at least 20 mol% of isophorone diisocyanate (IPDI) based on the total amount of polyisocyanates used.
11. The aqueous curable composition according to any of the above aspects, characterized in that the uretdione polyisocyanate a1 is prepared from isophorone diisocyanate as the only polyisocyanate used.
12. The aqueous curable composition according to any of the above aspects, characterized in that the uretdione polyisocyanate a1 contains 1 to 10 uretdione moieties.
13. Aqueous curable composition according to any of the preceding aspects, characterized in that compound a2 is at least one polyol, preferably at least one polyalkoxy ether derivative comprising at least two-OH groups, which are present on two different non-adjacent atoms of the molecule; and more preferably selected from compounds of formula (I):
Figure 445218DEST_PATH_IMAGE001
it is characterized in that
X is H or alkyl, preferably H or C1-20-alkyl, more preferably H or C2-10-an alkyl group;
r is C1-4An alkylene group;
p is an integer from 2 to 50;
in each unit p
n is independently 0 or 1 and
m is independently 0 or 1,
provided that at least one of n or m in each unit p is 1;
which is preferably characterized in that
X is H, methyl, ethyl or propyl, preferably ethyl;
r is methyl;
p is an integer from 5 to 25;
in each unit p
n is independently 0 or 1 and
m is independently 0 or 1,
provided that at least one of n or m in each unit p is 1 and that the total amount of n is ≧ m, preferably the total amount of n is at least 2 m, more preferably the total amount of n is at least 3 m, most preferably only n is present.
14. Aqueous curable composition according to any of the above aspects, characterized in that compound A3 is selected from at least one polyol different from a2, preferably from polyester polyols, polyether polyols, polyurethane polyols, polyacrylate polyols, polymethacrylate polyols, polycarbonate polyols or mixtures thereof, A3 is preferably selected from polyester polyols, polyether polyols, polycarbonate polyols, polyurethane polyols, polyacrylate polyols, polymethacrylate polyols, C having at least two hydroxyl groups2-C10-hydrocarbons or mixtures thereof, a3 being most preferably polyester polyols.
15. The aqueous curable composition according to any of the above aspects, characterized in that the compound a1 is used in an amount of 3.0 to 50.0 wt. -%, based on the total weight of compounds a1 to A3.
16. The aqueous curable composition according to any one of the preceding aspects, characterized in that the compound a2 is used in an amount of 50 to 97% by weight, based on the total weight of compounds a1 to A3.
17. The aqueous curable composition according to any of the above aspects, characterized in that the weight ratio of a1 to a2 is from 1: 1 to 1: 32.3.
18. The aqueous curable composition according to any of the above aspects, characterized in that the uretdione prepolymer is a dispersed uretdione prepolymer, preferably characterized in that the uretdione prepolymer is suspended in an aqueous liquid.
19. The aqueous curable composition according to any one of the preceding aspects, characterized in that the uretdione prepolymer a is contained in a total amount of 3 to 40 wt. -%, based on the total weight of the composition.
20. The aqueous curable composition according to any of the above aspects, characterized in that the azole compound C is at least one triazole compound selected from the group consisting of formula (III) or a salt thereof and formula (IV) or a salt thereof
Figure 848517DEST_PATH_IMAGE002
It is characterized in that
R1、R2、R3And R4Independently selected from a hydrogen atom, a halogen atom, a nitro group, a saturated or unsaturated aliphatic or cycloaliphatic radical, an optionally substituted aromatic radical comprising up to 20 carbon atoms and optionally up to 3 heteroatoms selected from oxygen, sulfur, nitrogen, an optionally substituted araliphatic radical comprising up to 20 carbon atoms and optionally up to 3 heteroatoms selected from oxygen, sulfur, nitrogen,
and R of formula (IV) is3And R4Together with the carbon atoms of the 1,2, 3-triazole anionic five-membered ring form a fused ring having 3 to 6 carbon atoms.
21. The aqueous curable composition according to aspect 20, characterized in that the azole compound C is selected from the group consisting of alkali metal-1, 2, 4-triazole salts, alkali metal-1, 2, 3-triazole salts, alkali metal-benzotriazole salts, alkaline earth metal-1, 2, 4-triazole salts, alkaline earth metal-1, 2, 3-triazole salts, alkaline earth metal-benzotriazole salts.
22. The aqueous curable composition according to any of the preceding aspects, characterized in that the at least one compound B comprising at least one Zerewitinoff-active group is selected from polyester polyols, polyether polyols, polyurethane polyols, polyacrylate polyols, polymethacrylate polyols or polycarbonate polyols and mixtures thereof.
23. The aqueous curable composition according to any one of the above aspects, characterized by containing the uretdione prepolymer A and
containing the at least one compound B comprising at least one Zerewitinoff-active group and
the triazole compound C is contained in an amount of 0.1 to 10 wt%, respectively based on the total weight of the composition.
24. The aqueous curable composition according to any of the above aspects, characterized in that the composition comprises water in an amount of 10 to 85 wt. -%, based on the total weight of the composition.
25. The aqueous curable composition according to any of the above aspects, characterized in that the pH value at 20 ℃ is from pH 5 to pH 13.
26. A method of curing a liquid composition on a substrate comprising
a) Applying an aqueous curable composition according to any one of aspects 1 to 25 on a substrate; and
b) exposing the deposited aqueous curable composition to a temperature of 60 ℃ to 160 ℃ to cure the deposited cured composition.
27. The method according to aspect 26, wherein the deposited aqueous curable composition is exposed to a temperature of 60 ℃ to 120 ℃ to cure the deposited cured composition.
28. The method according to aspect 26 or 27, wherein the deposited curable composition is exposed to the temperature for a time of 25 to 40 minutes to cure the deposited curable composition.
29. The method according to any one of aspects 26 to 28, wherein the deposited aqueous curable composition coalesces to form a coating.
30. The method according to any one of aspects 26 to 29, wherein the cured aqueous curable composition forms a solid on the substrate, preferably a transparent solid on the substrate.
31. A cured article obtainable by the method according to any one of aspects 26 to 30.
32. Use of a composition according to any one of aspects 1 to 25 for coatings, adhesives and/or sealants.
It has surprisingly been found that the above aqueous curable compositions cure at low temperatures, especially at 60 to 160 ℃, preferably 60 to 120 ℃, most preferably 80 to 100 ℃.
The aqueous curable composition contains less organic solvent than conventional curing compositions. According to the invention, water is used in the composition as a component (preferably as the main component) of the continuous liquid phase of the dispersion. The replacement of organic solvents, especially low VOC compounds, with water leads to more eco-friendly compositions. Preferred compositions according to the invention are characterized in that they comprise water in an amount of preferably 10 to 85% by weight, particularly preferably in an amount of 30 to 75% by weight, most preferably in an amount of 50 to 70% by weight, also preferably in an amount of 40 to 70% by weight, most preferably in an amount of 60 to 70% by weight, based in each case on the total weight of the composition.
The aqueous curable composition of the present invention has a preferred pH value (20 ℃) of pH 5 to pH13, more preferably pH 6 to pH 12, even more preferably pH 7 to pH 9.
Said reactant B of the composition comprises on average at least one Zerewitinoff-active group and may optionally be present. The Zerewitinoff-active group may also be reacted with a uretdione group. The uretdione prepolymer a may also react with itself, i.e. in the absence of B, to form a self-curable composition.
Thus, in one aspect, an aqueous curable composition comprises or consists of
A) At least one uretdione prepolymer comprising at least one uretdione group and being passable through
A1) At least one uretdione polyisocyanate having an isocyanate functionality of at least 2.0, whereby the uretdione polyisocyanate is obtained from at least one aliphatic polyisocyanate,
and
A2) at least one compound comprising at least one Zerewitinoff-active group, and
A3) at least one reactant comprising at least one Zerewitinoff-active group and being different from A2 or being H2O，
Preferably in the presence of at least one catalyst, to obtain a uretdione prepolymer;
wherein the prepolymer has an acid number of at most 4 mg KOH/g, preferably determined in the form of a 37% by weight aqueous dispersion according to DIN EN ISO2114: 2002-06; and
C) at least one azole compound, which preferably comprises at least one five-membered N-heterocycle, with the proviso that
(i) The five atoms forming the ring of the five-membered N-heterocyclic ring comprise a nitrogen atom in an amount of N = 1,2 or 3 and a carbon atom in an amount of (5-N),
(ii) the five-membered N-heterocycle contains two bridged double bonds and a delocalized negative charge.
At least one uretdione prepolymer comprising an average of at least one uretdione group (and preferably at least one Zerewitinoff-active group) is preferably dispersed in the aqueous continuous liquid phase. More preferably, the dispersed uretdione prepolymer is suspended in an aqueous liquid.
To further improve the physiological compatibility, the composition of the invention is preferably substantially free of compounds comprising at least one isocyanate group. Due to the presence of water in the composition, most up to all isocyanate groups will be hydrolysed. The content of isocyanate groups (expressed as NCO, M.G. 42 g/mol) is preferably less than 0.05% by weight. Particularly preferably, the composition of the present invention is free of compounds comprising at least one isocyanate moiety. Unless explicitly mentioned otherwise, the NCO content was determined according to the volume DIN-EN ISO11909 (DIN version of the latest version used at the filing date of the present application (or priority date, if applicable)).
In a preferred embodiment, the composition comprises said uretdione prepolymer in a total amount of from 1 to 50 wt. -%, preferably from 3 to 40 wt. -%, and most preferably from 30 to 40 wt. -%, based on the weight of the composition.
(measured and calculated as M by GPC as described above but using N, N-dimethylacetamide as the solvent instead of tetrahydrofuranwOf) uretdione prepolymerswPreferably in the range from 20,000 to 800,000 g/mol, particularly preferably in the range from 100,000 to 500,000 g/mol.
If the uretdione prepolymer exhibits an acid number of at most 4 mg KOH/g, preferably at most 3.5 mg KOH/g, more preferably 3.0 mg KOH/g, most preferably at most 2.5 mg KOH/g, each determined according to DIN EN ISO2114:2002-06 (based on the total weight of the sample prepared to be used as starting compound to be tested in the determination according to DIN EN ISO2114: 2002-06), the curing time is significantly reduced. The units of the acid number according to the DIN EN ISO2114:2002-06 are the amount of KOH in mg per g of the sample. The sample consists essentially of (or consists of) 37 wt.% of a uretdione prepolymer and water.
The acid number of each uretdione prepolymer sample was always determined according to DIN EN ISO2114: 2002-06. Instead of a mixture of toluene and ethanol as described in DINEN ISO2114:2002-06, a 2:1 weight ratio mixture of acetone and ethanol was used.
The acid number according to the invention is preferably at most 10.8 mg KOH/g, more preferably at most 9.5 mg KOH/g, particularly preferably 8.1 mg KOH/g, most preferably at most 6.8 mg KOH/g, referred to the weight of the amount of uretdione prepolymer itself. In these preferred embodiments, the unit of acid number is the calculated amount of KOH in mg per g of uretdione prepolymer. The determination was also carried out using the above-mentioned samples as initial compounds for determining the acid number (see above).
Preferably the composition comprises at least one uretdione prepolymer exhibiting a zeta potential of-20 mV or higher.
The zeta potential of the uretdione prepolymers was determined from their dispersion in water as a sample. 1 drop of the uretdione prepolymer preformed dispersion was highly diluted with 20 ml of demineralized water and homogenized by stirring to give a sample. The zeta potential was subsequently determined in a Malvern Nanosizer ZS90 instrument (Malvern Instruments, Herrenberg, Germany) at 23 ℃. The given values of zeta potential always relate to the sample in which the uretdione polymer is dispersed.
Preferably, the uretdione prepolymer is a nonionic prepolymer.
It has also been found that the cure time is improved by incorporating hydrophilic groups as grafts or termini into the structure of the uretdione prepolymer. For the reasons outlined above, the hydrophilic group is still preferably free of ionic moieties. Preferred uretdione prepolymers comprise grafts having at least one hydrophilic group selected from a polyalkylene oxide ether terminated with a methyl, ethyl, propyl or butyl group, a polyethylene oxide terminated with a methyl group, a polyethylene oxide terminated with an ethyl, propyl or butyl group. Particularly preferred uretdione prepolymers additionally comprise an average of at least one a-O- (CH)2CH2O)n-R moiety, wherein R means (C)1-C4) -alkyl and n denotes a number from 3 to 100, n preferably denotes a number from 5 to 70, more preferably from 7 to 55. R is preferably methyl.
The hydrophilic groups can be introduced into the structure of the uretdione prepolymers by means of compound a2, preferably as hydrophilicizing agent, more preferably nonionic. Suitable nonionically hydrophilicizing agents are, for example, polyalkylene oxide ethers having isocyanate-reactive groups, such as hydroxyl, amino or thiol groups. Suitable examples are monohydroxy-functional polyalkylene oxide polyether alcohols having, on statistical average, from 5 to 70, preferably from 7 to 55, ethylene oxide units per molecule, which are obtainable in a manner known per se by alkoxylation of suitable starter molecules (for example in Ullmanns encyclopedia ä der technischen Chemie [ Ullmanns encyclopaedia of industrial chemistry ], 4 th edition, volume 19, Verlag Chemie, Weinheim, pages 31 to 38). These are pure polyethylene oxide ethers or mixed polyethylene oxide ethers, wherein they contain at least 30 mol%, preferably at least 40 mol%, of ethylene oxide units, based on all alkylene oxide units present.
Particularly preferred nonionically hydrophilizing agents are monofunctional mixed polyalkylene oxide polyethers having from 40 to 100 mol% of ethylene oxide units and from 0 to 60 mol% of propylene oxide units.
Suitable starter molecules for such nonionically hydrophilicizing agents are, in particular, saturated monoalcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomeric pentanols, hexanols, octanols and nonanols, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanols or hydroxymethylcyclohexanes, 3-ethyl-3-hydroxymethyloxetane or tetrahydrofurfuryl alcohol, diethylene glycol monoalkyl ethers, such as diethylene glycol monobutyl ether, unsaturated alcohols, such as allyl alcohol, 1-dimethylallyl alcohol or oleyl alcohol, aromatic alcohols, such as phenol, the isomeric cresols or methoxyphenols, araliphatic alcohols, such as benzyl alcohol, anisyl alcohol or cinnamyl alcohol, secondary monoamines, such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, bis (2-ethylhexyl) amine, N-methyl-and N-ethylcyclohexylamine or dicyclohexylamine, and also heterocyclic secondary amines, such as morpholine, pyrrolidine, piperidine or 1H-pyrazole. Preferred starter molecules are saturated monoalcohols of the type described above. Particular preference is given to using diethylene glycol monobutyl ether or n-butanol as starter molecule. Alkylene oxides suitable for the alkoxylation reaction are, in particular, ethylene oxide and propylene oxide, which can be used in any desired sequence or in a mixture for the alkoxylation reaction.
Another preferred class of hydrophilizing agents is polymers having two OH groups and polyalkylene oxide side groups, for example polyether-1, 3-diols. Commercially available examples are Ymer N120 (CAS number: 131483-27-7) and Tegomer D3403 (Evonik Industries AG, Essen, DE) from Perstorp Holding AB, Malm miniature, Sweden.
The uretdione prepolymer exhibits an acid number of at most 4 mg KOH/g (preferably at most 3.5 mg KOH/g, particularly preferably 3.0 mg KOH/g, most preferably 2.5 mg KOH/g) and comprises at least one uretdione group: furthermore, on average at least one Zerewitinoff-active radical, particularly preferably at least two hydroxyl groups and at least one a-O- (CH)2CH2O)n-R moiety, wherein R means a hydrogen atom or (C)1-C4) -alkyl and n denotes a number from 3 to 100, n preferably denotes a number from 5 to 70, more preferably from 7 to 55. R is preferably methyl.
The uretdione prepolymer includes at least one uretdione group. Preferably, the uretdione prepolymer comprises at least two uretdione groups. The preferred uretdione prepolymers of the present invention are self-curing prepolymers. During the heat-induced curing, the uretdione prepolymers will (self) crosslink by reaction of the uretdione groups with the Zerewitinoff-active groups. The more uretdione groups and Zerewitinoff-active groups that are contained on average in the uretdione prepolymer (or the reactants) the better.
A "Zerewitinoff-active group" is defined as a functional group comprising at least one Zerewitinoff-active hydrogen atom, i.e. an acidic hydrogen atom or an active hydrogen atom.
The abundance of such active hydrogen atoms is determined by known reactions of the compounds with grignard reagents. The amount of Zerewitinoff active hydrogen atoms is usually determined by measuring the amount of methane gas released and is subsequently calculated taking into account the stoichiometry of the following reaction equation, in which for each mole of active hydrogen atoms of the compound (R-XH) 1 mole of methyl magnesium bromide (CH) is used3MgBr) and release 1 mol of methane:
CH3-MgBr + R-XH → CH4+ Mg (XR)Br
zerewitinoff-active radicals, in particular C-H-active organic radicals, -OH, -SH, -NH2or-NHR ', wherein R' refers to an organic moiety. The Zerewitinoff-active group is preferably selected from the group consisting of-OH, -SH, -NH2or-NHR ', wherein R' refers to an organic moiety. Particularly preferably, the Zerewitinoff-active groups according to the invention are selected from-OH. Particularly preferred uretdione prepolymers contain at least two hydroxyl groups as Zerewitinoff-active groups.
The preparation of the uretdione prepolymers is generally effected by reacting the uretdione polyisocyanates with at least one compound comprising at least two Zerewitinoff-active groups using standard reaction techniques. It has been found that it is even possible to cure at low temperatures uretdione prepolymers prepared from at least one aliphatic uretdione polyisocyanate (in particular a cycloaliphatic uretdione polyisocyanate), preferably from at least 20 mol%, based on the total amount of polyisocyanate used, of an aliphatic uretdione polyisocyanate, particularly preferably from aliphatic uretdione polyisocyanates alone.
Uretdione polyisocyanate a1 is used in an amount of 3 to 50% by weight of the total amount of reactants used to prepare the dispersed uretdione prepolymer.
Compound a2 having at least one Zerewitinoff-active group is preferably used in an amount of from 50 to 97% by weight of the total amount of reactants used for preparing the dispersed uretdione prepolymer.
For the preparation of the dispersed uretdione prepolymers, particular preference is given to using uretdione polyisocyanates A1: the compounds A2 in a weight ratio of from 1: 1 to 1: 32.3.
Uretdione polyisocyanate a1 is typically obtained by catalytic dimerization of polyisocyanates via methods known in the art. Examples of suitable polyisocyanates include diisocyanates such as linear aliphatic polyisocyanates, cycloaliphatic polyisocyanates, and alkylaryl polyisocyanates. Specific examples include 1, 4-diisocyanatobutane, 1, 5-diisocyanatopentane (PDI), 1, 6-diisocyanatohexane (also known as HDI or 1, 6-hexamethylene diisocyanate), 2,4 '-and/or 4,4' -diisocyanatocyclohexylmethane (HMDl), isophorone diisocyanate (IPDI), 1, 3-and 1, 4-diisocyanatomethylcyclohexane, 1, 3-and 1, 4-Xylylene Diisocyanate (XDI), and mixtures thereof.
Examples of dimerization catalysts are: trialkylphosphines, aminophosphines and aminopyridines, such as dimethylaminopyridine, and tris (dimethylamino) phosphine, and any other dimerization catalyst known to those skilled in the art.
The result of the dimerization reaction depends, in a manner known to the skilled worker, on the catalyst used, on the process conditions and on the polyisocyanate used. It is possible in particular to form products which contain on average more than one uretdione group per molecule, a distribution of the number of uretdione groups being present. Preferred uretdione compounds are prepared by catalytic dimerization of HDI and/or IPDI.
The uretdione polyisocyanates A1 preferably contain on average from 1 to 10 uretdione moieties.
The uretdione polyisocyanate A1 is preferably prepared from isophorone diisocyanate (IPDI), 1, 6-diisocyanatohexane (also known as HDI or 1, 6-hexamethylene diisocyanate) or mixtures thereof.
The uretdione polyisocyanate A1 is preferably prepared from at least one cycloaliphatic polyisocyanate. In a further preferred embodiment, the uretdione polyisocyanate A1 is prepared from at least 20 mol% of isophorone diisocyanate (IPDI), based on the total amount of polyisocyanates used. The uretdione polyisocyanate A1 is most particularly preferably prepared from isophorone diisocyanate as the only polyisocyanate used.
Preferred uretdione polyisocyanates are available, for example, as Desmodur N3400 from CovestroDeutschland AG, Leverkusen, Germany.
As mentioned above, the polyuretdione prepolymer is prepared from at least one uretdione polyisocyanate a1 and at least one compound a 2.
The compound A2 is particularly preferably selected from at least one polyol. Preferred curable compositions according to the invention comprise at least one uretdione prepolymer, which is prepared by reaction of at least one uretdione polyisocyanate a1 as defined above with a compound a2 selected from at least one polyol.
The term "polyol" is intended to include materials having an average of two or more primary hydroxyl groups per molecule. Polyols useful in practice may be low or high molecular weight materials and will generally have an average hydroxyl number as determined by ASTM designation E-222-67, method B, of from about 1000 to 2, and preferably from about 500 to 2. Polyols include low molecular weight diols, triols, and higher alcohols and polymeric polyols, such as polyester polyols, polyether polyols, polyurethane polyols, and hydroxyl-containing (meth) acrylic polymers.
The at least one polyol as compound A2 is preferably selected from polyester polyols, polyether polyols, polyurethane polyols, polycarbonate polyols, polyacrylate polyols, polymethacrylate polyols, C having at least two hydroxyl groups2-C10-a hydrocarbon or a mixture thereof.
Low molecular weight diols, triols and higher alcohols useful in the present invention are known in the art. They are mostly monomeric and have hydroxyl numbers of 200 and higher, typically in the range of 1500 to 200. Such materials include aliphatic polyols, particularly alkylene polyols containing from 2 to 18 carbon atoms. Examples include ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol; alicyclic polyols such as cyclohexanedimethanol. Examples of trihydric and higher alcohols include trimethylolpropane and pentaerythritol. Polyols containing ether linkages (ether linkages) such as diethylene glycol and triethylene glycol are also useful.
Most suitable polymeric polyols are those having a hydroxyl number of less than 200, such as from 10 to 180. Examples of the polymeric polyol include polyalkylene ether polyols, polyester polyols (including hydroxyl-containing polycaprolactones), hydroxyl-containing (meth) acrylic polymers, polycarbonate polyols, and polyurethane polyols.
Examples of polyether polyols are poly (oxytetramethylene) glycol, poly (oxyethylene) glycol, poly (oxypropylene) glycol, and the reaction products of ethylene glycol with mixtures of propylene oxide and ethylene oxide.
Polyether polyols formed by the oxyalkylation of various polyols, for example, diols such as ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, and the like, or higher polyols such as trimethylolpropane, pentaerythritol, and the like, are also useful. One common oxyalkylation method is to react a polyol with an alkylene oxide, such as ethylene oxide, in the presence of an acidic or basic catalyst.
Polyester polyols may also be used as the polymeric polyol component in the practice of the present invention. The polyester polyols can be prepared by polyesterification of organic polycarboxylic acids or anhydrides thereof with organic polyols. Typically, the polycarboxylic acids and polyols are aliphatic or aromatic dibasic acids and diols.
Diols commonly used in the manufacture of polyesters include alkylene glycols such as ethylene glycol and butylene glycol, neopentyl glycol and other glycols such as cyclohexanedimethanol, caprolactone glycols (e.g., the reaction product of caprolactone and ethylene glycol), polyether glycols such as poly (oxytetramethylene) glycol, and the like. However, other types of diols and (as shown) higher functionality polyols may also be utilized. Such higher polyols preferably include, for example, trimethylolpropane, trimethylolethane, pentaerythritol, and the like, as well as higher molecular weight polyols, such as those made by the oxyalkylation of low molecular weight polyols. A particularly preferred example of such a high molecular weight polyol is the reaction product of 20 moles of ethylene oxide per mole of trimethylolpropane.
The acid component of the polyester polyol consists essentially of monomeric carboxylic acids or anhydrides having from 2 to 18 carbon atoms per molecule. Useful acids are phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, glutaric acid, chlorendic acid, tetrachlorophthalic acid and various types of other dicarboxylic acids. Higher polycarboxylic acids such as trimellitic acid and tricarballylic acid may also be employed (where acids are mentioned hereinabove, it is to be understood that anhydrides of those acids which form anhydrides may be used in place of the acids). Lower alkyl esters of acids, such as dimethyl glutarate, may also be used.
In addition to polyester polyols formed from polybasic acids and polyols, polycaprolactone-type polyesters may also be used. These products are formed from the reaction of a cyclic lactone (such as caprolactone) with a polyol having primary hydroxyl groups (such as those mentioned above). Such a product is described in U.S. patent No. 3,169,945 to hosettler.
In addition to polyether polyols and polyester polyols, (meth) acrylic polymers or (meth) acrylic polyols containing hydroxyl groups can also be used as the polyol component.
Among the (meth) acrylic polymers are polymers having from about 2 to 20 weight percent of primary hydroxyl containing vinyl monomers (e.g., hydroxyalkyl acrylates and methacrylates having from 2 to 6 carbon atoms in the alkyl group) and from 80 to 98 weight percent of other ethylenically unsaturated copolymerizable materials such as alkyl (meth) acrylates; the weight percentages are based on the total weight of the monomer feed.
Examples of suitable hydroxyalkyl (meth) acrylates are hydroxyethyl (meth) acrylate and hydroxybutyl (meth) acrylate. Examples of suitable alkyl acrylates and alkyl (meth) acrylates are lauryl methacrylate, 2-ethylhexyl methacrylate and n-butyl acrylate.
In addition to the acrylates and methacrylates, other copolymerizable monomers copolymerizable with the hydroxyalkyl (meth) acrylates are ethylenically unsaturated materials, such as mono-and diolefins, halogenated mono-and diolefins, unsaturated esters of organic and inorganic acids, amides and esters of unsaturated acids, nitriles and unsaturated acids, and the like. Examples of such monomers include styrene, 1, 3-butadiene, acrylamide, acrylonitrile, alpha-methylstyrene, alpha-methylchlorostyrene, vinyl butyrate, vinyl acetate, alkyl chlorides, divinylbenzene, diallyl itaconate, triallyl cyanurate and mixtures thereof. These other ethylenically unsaturated materials are typically used in admixture with the acrylates and methacrylates mentioned above.
In a particularly preferred embodiment of compound a2, compound a2 is selected from polyester polyols, polyether polyols, polycarbonate polyols, polyurethane polyols, polyacrylate polyols, polymethacrylate polyols, C having at least two hydroxyl groups2-C10-hydrocarbons or mixtures thereof, wherein said compound a2 comprises at least one a-O- (CH)2CH2O)n-R moiety, wherein R means (C)1-C4) -alkyl and n denotes a number from 3 to 100. n preferably means a number from 5 to 70, more preferably from 7 to 55. R is preferably methyl.
Further suitable compounds A2 are selected from compounds of the formula (I)
X–O–(CH2CH2O)n–R (I)
Wherein
X is a straight-chain dihydroxy (C)3-C10) Alkyl, branched dihydroxy (C)3-C10) Alkyl or monohydroxy (C)2-C6) -an alkyl group,
r is a hydrogen atom or (C)1-C4) -alkyl, and
n is a number from 3 to 100.
In formula (I), X preferably means bis (hydroxymethyl) - (C)1-C8) Alkyl or branched bis (hydroxymethyl) - (C)1-C8) -an alkyl group. Particularly preferred X of formula (I) is bis (hydroxymethyl) - (C)1-C8) Alkyl or branched bis (hydroxymethyl) - (C)1-C8) -alkyl, provided that both hydroxymethyl groups are separately bonded to the same carbon atom.
In formula (I), n preferably means a number from 5 to 70, more preferably from 7 to 55. In formula (I), R preferably means methyl.
In a particularly preferred embodiment of the present invention, the dispersed uretdione prepolymer is prepared from compound a2, which is a combination of at least one polyalkylene oxide ether having isocyanate-reactive groups, such as hydroxyl, amino or thiol groups (preferably at least one compound of formula (I) mentioned above) and at least one polyol polymer. According to this embodiment, the dispersed uretdione prepolymer is also preferably prepared from a combination of
A2-1) at least one compound of the formula (I)
X–O–(CH2CH2O)n–R (I)
Wherein
X represents a hydrogen atom or a linear dihydroxy group (C)3-C10) Alkyl or branched dihydroxy(s) ((iii))C3-C10) -an alkyl group,
r is (C)1-C4) -alkyl, preferably methyl and
n is a number from 3 to 100, preferably from 8 to 30,
and
A3) at least one polyol different from A2 selected from polyester polyols, polycarbonate polyols, polyurethane polyols, polyacrylate polyols, polymethacrylate polyols or mixtures thereof.
Most preferably, compound a2-1 is used in a total amount of 1 to 25 wt.%, preferably 5 to 20 wt.%, and compound A3 is used in a total amount of 20 to 70 wt.%, preferably 35 to 65 wt.%, based on the total amount of reactants used to prepare the dispersed uretdione prepolymer.
Preferably, a portion of the isocyanate groups of uretdione polyisocyanate A1 is first reacted with compound A2-1 to yield a polyurethane having at least one x-O- (CH)2CH2O)nThe uretdione polyisocyanates of the moiety R and secondly the remaining isocyanate groups of the above reaction product are reacted with compound A3 to give the final uretdione prepolymer.
In a preferred aspect, compound a3 is water.
In another aspect of the invention, reactant B is present and may be selected from at least one compound comprising on average at least one Zerewitinoff-active group. Reactant B is preferably selected from at least one polyol, particularly preferably from at least one polymeric polyol, most preferably from at least one of the preferred polymeric polyols as defined above for a2 (see above).
Alternatively, preferred compositions of the invention comprise at least one reactant B, wherein the reactant is selected from polyester polyols, polyether polyols, polycarbonate polyols, polyurethane polyols, polyacrylate polyols, polymethacrylate polyols, C having at least two hydroxyl groups2-C10-a hydrocarbon or a mixture thereof.
The curable composition of the present invention comprises as component C at least one azole compound. According to the Hantzsch-Widman nomenclature (IUPAC-rules RB-1.2, R-2.3.3.1), oxazole (azole) is a general term for unsaturated five-membered heterocyclic compounds containing one nitrogen atom in the ring and, optionally, in addition, at least one or more additional heteroatoms (including nitrogen atoms). The azole compound according to the present invention also includes a salt thereof (azole).
Preferred azole compounds comprise five-membered N-heterocycles. The preferred N-heterocyclic ring contains N nitrogen atoms in an amount of N = 1,2 or 3 and carbon atoms in an amount of (5-N). In addition, the five-membered ring of the N-heterocycle contains two bridged double bonds. The bridged double bonds are preferably conjugated double bonds. The five-membered N-heterocycle is negatively charged. The negative charge is delocalized. Preferably, the bridged ring double bond contributes to delocalization of the negative charge.
Preferably the composition comprises at least one azole compound of formula (II)
Figure 638619DEST_PATH_IMAGE003
Wherein
X1、X2、X3And X4Represents, independently of one another, "-N =" fractions in which X1、X2、X3And X4Represents "-CR =" independently of each other, wherein R independently represents H, C1To C20Alkyl radical, C3To C20Cycloalkyl radical, C6To C20Aryl radical, C1To C2Alkoxy, -NR'2（R'=C1To C20Alkyl), -NO2Fluorine, chlorine, bromine, fluorinated C1-C6Alkyl, fluorinated C1-C6-alkoxy, cyano, alkoxycarbonyl (carboalkoxy), -S-R "(R" = C)1To C20Alkyl) and/or-S- (C)6To C20Aryl) and at X)1To X4In the case that two adjacent substituents represent "-CR =", the R substituents of these substituents together with the C atom of these substituents may form a further cyclic (annellated) carbocyclic or heterocyclic n-membered ring system, wherein n =3 to 10, which isThe mesocyclic carbocyclic or heterocyclic ring system may contain, independently of each other, one or more heteroatoms (N, O, S) and may be substituted, independently of each other, by one or more identical or different substituents selected from the group consisting of: H. c1To C20Alkyl radical, C3To C20Cycloalkyl radical, C6To C20Aryl radical, C1To C2Alkoxy, -NR'2（R'=C1To C20Alkyl), -NO2Fluorine, chlorine, bromine, fluorinated C1-C6Alkyl, fluorinated C1-C6-alkoxy, cyano, alkoxycarbonyl, -S-R "(R" = C)1To C20Alkyl) and/or-S- (C)6To C20Aryl), Cat)+Is a counter ion.
The ring of formula (II) represents a pi-system comprising two bridged ring double bonds and a delocalized charge.
Azole compounds are generally prepared by deprotonation of neutral azole compounds. Deprotonation is preferably effected with a base, preferably with an alkali metal alkoxide, such as sodium methoxide, alkaline earth metal alkoxide, alkali metal hydroxide or alkaline earth metal hydroxide. The azole compounds of the formula (II) are preferably prepared by deprotonation of the neutral compounds of the formula (II-1) with a base, preferably with at least one of the preferred bases mentioned above.
Figure 422642DEST_PATH_IMAGE004
Wherein X1、X2、X3And X4Defined according to formula (II).
Other suitable neutral compounds for preparing the azole compounds according to the invention include pyrrole, substituted pyrroles and carbocyclic and/or heterocyclic ring-formed derivatives of pyrrole.
Other suitable neutral compounds for preparing the azole compounds according to the invention include pyrazole and/or imidazole, substituted pyrazole and/or imidazole, and carbocyclic and/or heterocyclic ring-annulated derivatives of pyrazole and/or imidazole.
Other suitable neutral compounds for preparing the azole compounds according to the invention include triazoles, preferably substituted species selected from the group consisting of 1,2, 3-and 1,2, 4-triazoles, 1,2, 3-and 1,2, 4-triazoles and carbocyclic and/or heterocyclic cyclized species of 1,2, 3-and 1,2, 4-triazoles.
To produce azole compounds, in principle all five-membered N-heterocycles having at least one hydrogen atom bonded to a ring nitrogen atom can be used. Examples of these include pyrrole, indole, carbazole and substituted derivatives such as 5-nitroindole or 5-methoxyindole, pyrazole, indazole and substituted derivatives such as 5-nitroindazole, imidazole and substituted derivatives such as 4-nitroimidazole or 4-methoxyimidazole, benzimidazole or substituted benzimidazole, for example 5-nitrobenzimidazole, 5-methoxybenzimidazole, 2-trifluoromethylbenzimidazole, heteroaromatic annulated imidazoles such as pyridoimidazole or purine, 1,2, 3-triazole and substituted derivatives such as 4-chloro-5-methoxycarbonyl-1, 2, 3-triazole or 4-chloro-5-cyano-1, 2, 3-triazole, 1,2, 4-triazole and substituted derivatives such as 3, 5-dibromotriazole, 1,2, 3-benzotriazole and substituted 1,2, 3-benzotriazoles such as 5-fluoro-1, 2, 3-benzotriazole, 5-trifluoromethyl-1, 2, 3-benzotriazole, 5-nitro-1, 2, 3-benzotriazole, 5-methoxy-1, 2, 3-benzotriazole, 5-chloro-1, 2, 3-benzotriazole, 5-tetrafluoroethoxy-1, 2, 3-benzotriazole, 5-trifluorothio-1, 2, 3-benzotriazole, 4, 6-bis- (trifluoromethyl) -1,2, 3-benzotriazole, 4-trifluoromethoxy-5-chloro-1, 2, 3-benzotriazole and heteroaromatic cyclized 1,2, 3-triazoles, such as the isomeric pyridotriazoles, for example 1H-1,2, 3-triazolo [4,5-b ] pyridine-are referred to hereinafter as pyridotriazole-and azapurines.
In a particularly preferred composition of the invention, the composition comprises at least one triazole compound as component C).
The triazole compound is most preferably at least one triazole compound selected from the group consisting of formula (III) and formula (IV)
Figure 894074DEST_PATH_IMAGE005
Wherein
R1、R2、R3And R4Independently of one another, means a hydrogen atom, a halogen atom, a nitro group, a saturated or unsaturated aliphatic radical orA cycloaliphatic group, an optionally substituted aromatic group comprising up to 20 carbon atoms and optionally up to 3 heteroatoms selected from oxygen, sulfur, nitrogen, an optionally substituted araliphatic group comprising up to 20 carbon atoms and optionally up to 3 heteroatoms selected from oxygen, sulfur, nitrogen, and wherein R of formula (IV)3And R4Together with the carbon atoms of the 1,2, 3-triazole anionic five-membered ring form a fused ring having 3 to 6 carbon atoms.
The triazole compounds are particularly preferably selected from the group consisting of alkali metal-1, 2, 4-triazoles, alkali metal-1, 2, 3-triazoles, alkali metal-benzotriazoles, alkaline earth metal-1, 2, 4-triazoles, alkaline earth metal-1, 2, 3-triazoles and alkaline earth metal-benzotriazoles. Particularly preferably, the triazole compound is selected from alkali metal-1, 2, 4-triazole salts, alkali metal-1, 2, 3-triazole salts, alkali metal-benzotriazole salts. Sodium 1,2, 4-triazole, potassium 1,2, 4-triazole, sodium 1,2, 3-triazole, potassium 1,2, 3-triazole, sodium benzotriazole, potassium benzotriazole and mixtures thereof are the most preferred triazole compounds.
It has proven advantageous to apply preferably a curable composition comprising the azole compound, preferably the triazole compound, in an amount of 0.1 to 10.0 wt.%, particularly preferably 0.3 to 3 wt.%, respectively, based on the weight of the composition. Particularly preferred curable compositions of the invention comprise the dispersed uretdione prepolymer in an amount of from 1 to 50 wt.%, preferably from 3 to 40 wt.%, and most preferably from 30 to 40 wt.%, and the azole compound, preferably the triazole compound, in an amount of from 0.1 to 10.0 wt.%, preferably from 0.3 to 3 wt.%, respectively, based on the weight of the composition.
The above compositions may contain various optional ingredients in addition to the ingredients mentioned. Examples of these are dyes, pigments, fillers and reinforcing agents, for example calcium carbonate, silicates, talc, kaolin, mica and barium sulfate. Other additives such as plasticizers, lubricants and rheological additives and solvents or diluents may be included in the composition. When present, these optional ingredients may constitute up to 50 weight percent of the composition, based on the total weight of the composition.
Of particular interest is the use of the compositions of the present invention for the preparation of coatings on various types of substrates. These coatings are preferably protective coatings and decorative coatings, such as topcoats on various types of substrates (e.g. buildings, fences, particle boards), and coatings such as on stone, concrete or metal, for coatings for vehicles (e.g. cars, railways or aircraft). The compositions are likewise useful for automotive OEM coating and automotive refinish (refinish), and for the coating of vehicle bodies, automotive plastic parts and vehicle body-mounted automotive parts (finishing).
The compositions of the present invention may also be used as sealants or adhesives.
Another object of the invention is a method for curing a liquid composition on a substrate comprising
a) Applying an aqueous curable composition according to the present invention on a substrate; and
b) exposing the deposited aqueous curable composition to a temperature of 60 ℃ to 160 ℃ to cure the deposited cured composition.
The aqueous curable composition can be uniformly applied to a substrate using known coating methods, for example, by spin coating, dip coating, knife coating, curtain coating, brush coating, spray coating (especially electrostatic spray coating), and reverse roll coating. The paint composition may be used as a primer, a color coat or a clear coat.
The above-described preferred embodiments of the aqueous curable composition are of course also preferably used in the process of the present invention.
In a particular embodiment of the process, prior to step a), the aqueous curable composition of step a) is prepared from an aqueous curable concentrate comprising
i) 25 to 50 wt.%, preferably 32 to 45 wt.%, of at least one uretdione prepolymer A,
and
ii) 0.1 to 10% by weight, preferably 0.3 to 5% by weight, of at least one azole compound C,
to produce an aqueous curable composition for use in step a), said aqueous curable composition comprising, relative to the weight of the aqueous curable composition of step a)
i) 12.5 to 42.2% by weight, preferably 27 to 38% by weight, of at least one uretdione prepolymer A,
and
ii) 0.05 to 8.5 wt.%, preferably 0.25 to 3 wt.%, of at least one azole compound.
The choice and concentration of the diluent depends primarily on the choice of coating ingredients and the coating method. The diluent should be inert. In other words, it should not undergo any chemical reaction with the components and should be capable of being removed during curing after the coating operation. It has surprisingly been found that water is especially a suitable diluent. Examples of suitable diluents are water, ketones, ethers and esters, such as methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, N-methylpyrrolidone, dioxane, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 1, 2-dimethoxyethane, ethyl acetate, N-butyl acetate and ethyl 3-ethoxypropionate. It is particularly preferred to use water as the maximum amount of diluent.
It is particularly preferred that the deposited aqueous curable composition coalesces to form a coating. The coating thickness after drying is usually 0.5 to 46 μm. If the coating is a base coat, the coating thickness after drying is preferably 15 to 20 μm. If the coating is a top coat (top coat), the coating thickness after drying is preferably 45 to 50 μm.
The deposited aqueous curable composition is preferably exposed to a temperature of from 60 to 120 ℃, preferably from 80 to 100 ℃, to cure the deposited cured composition.
According to the method of the present invention, the deposited aqueous curable composition is preferably exposed to said temperature for a time of from 20 to 45 minutes to cure said deposited cured composition. It is particularly preferred to expose the deposited aqueous curable composition to a temperature of from 60 to 120 c, preferably from 80 to 100 c, for a period of from 20 to 45 minutes.
It is also preferred to cure the deposited aqueous curable composition by preheating the deposited curable composition to a temperature of from 30 ℃ to less than 60 ℃ for a time of from 2 to 10 minutes. It is particularly preferred after said preheating to increase the temperature to 60 to 160 ℃ (preferably to 60 to 120 ℃, most preferably to 80 to 100 ℃) and to expose it to said increased temperature for a further period of time of 20 to 45 minutes. The preheating step is advantageous because the amount of water in the deposited curable composition is reduced prior to curing. Thereby enhancing the subsequent curing reaction at 60 ℃ to 160 ℃.
Preferably, the cured aqueous curable composition forms a crosslinked film on a substrate that exhibits excellent mechanical and optical properties and high resistance to chemicals and solvents.
Examples
The invention is illustrated with reference to examples, which should not be construed as limiting. Unless otherwise specified, all quantitative data, fractions and percentages are on a weight basis, and the total amounts relate to the total weight of the composition.
1. The method and the material are as follows:
all percentages are by weight unless otherwise specified.
1.1 pendulum hardness:
the pendulum hardness by the kining method was measured on glass plates according to DIN EN ISO 1522: 2007-04.
1.2 solvent resistance and Water resistance:
the cured coatings were tested for resistance to xylene, 1-methoxy-2-propyl acetate, ethyl acetate, acetone, and water. A piece of cotton wool saturated with the test substance was placed on the coated surface and covered with a watch glass. After the indicated exposure time, the lint was removed, and the exposed area was allowed to dry and immediately inspected. The evaluation of the softening or discoloration of the coating surface was carried out in accordance with DIN EN ISO 4628-1: 2016-07.
0: constant, i.e. no perceptible change
1 very slight, i.e. only visible, change, e.g. slight discoloration
Recognizable, i.e. clearly recognizable, changes, e.g. noticeable softening in case of fingernail scribing
Clearly noticeable changes, e.g. moderate discoloration, possibly minor blistering
4: strong change, e.g. severe foaming
5: complete destruction of the coating without external influence.
1.3 infrared measurement:
uretdione ring opening was characterized by FT-IR spectroscopy (tensor II from Bruker with Platinum ATR unit (diamond crystal)). At (4000--1The spectrum is recorded in the wavenumber range of (a). Evaluation of uretdione Peak (about 1760 cm)-1) Is measured. The peak heights of the comparative systems were compared with the initial values (uretdione film without catalyst, dried at room temperature) set to 100% and the changes relative thereto (ratio formation). The uretdione peak height of the film cured at 180 ℃ for 30 minutes was set to 0%.
When measured on an ATR crystal, the intensity of the spectrum depends on the occupancy of the crystal surface. Since a comparable coverage of the crystal surface cannot be ensured by the sample preparation in the case of different measurements, it is necessary to determine the peak values of all spectra at the CH stretching vibration (wave number range 3000 and 2800 cm)-1) The above normalization is performed to correct for this effect on ratio formation. In the case where the peak height is evaluated as described above, baseline correction of the spectrum is additionally performed.
1.4 measurement of oscillation:
rheometer Rheometrics ARES. Measurements were performed in oxygen-exclusion (convection oven with nitrogen). Sample preparation was performed in a Teflon-Petry dish. Circular samples of 14mm diameter were punched out from the dried film (24 hours at room temperature in air). The rheometer oven is preheated to a measurement temperature (e.g., 160 ℃). A few seconds before the measurement, the furnace was opened, the cut sample was inserted between 14mm diameter circular measurement plates, the furnace was closed and the measurement plates collapsed until the sample height filled the measurement gap and a clear increase in normal force was observed. Immediately thereafter, the time measurement was started and the storage modulus G' as a function of the measurement time was determined at a constant sample temperature. The measuring frequency is 1 Hz.
1.5 catalyst:
reference systems not according to the invention
Lupragen N700 (Cat 1) (or DBU or 1, 8-diazabicyclo-5, 4, 0-undecene-7) was purchased from BASF SE, Ludwigshafen, Germany.
Polycat SA2LE (Cat 2) (occluded DBU) was purchased from Air Products GmbH, Hattingen, Germany (now Evonik).
The invention
Triazole-catalysts were purchased from Sigma-Aldrich Chemie GmbH, Munich, Germany. If triazole (amine form) is commercially available, the triazole catalyst is prepared as follows: 1 mole of catalyst (amine form) was slurried in water (10%), followed by the addition of 1 mole of NaOH (solid) or KOH, LiOH, RbOH, CsOH and stirring until a clear liquid formed.
The triazole catalyst solution used had the following specifications:
aqueous solution:
1,2, 3-Triazolesulfonate having a solid content of 24.0% and a pH of 11.5
1,2, 4-Triazolesulfonate having a solid content of 12.4% and a pH of 12.3
Sodium benzotriazole with a solid content of 20.5% and a pH of 10.9
1,2, 4-Triazolithium with a solids content of 9.9% and a pH of 11.7
1,2, 4-Triazolesutassium phosphate with a solid content of 26.0% and a pH of 11.7
1,2, 4-Cesium triazolate, solid content 43.6%, pH 13.9
1,2, 4-Triazolidinium with a solid content of 1.5% and a pH of 11.3.
2.0 Polymer Synthesis example:
all analytical measurements refer to measurements at a temperature of 23 ℃ unless otherwise indicated.
The solids content (non-volatile content) was determined by heating a weighed sample to constant weight at 125 ℃. The solids content was calculated by reweighing the sample at constant weight.
The NCO content was determined by volume according to DIN-EN ISO 11909: 2007-05. By means of infrared spectroscopy (at 2260 cm)-1Band of (ii) to control free NCO groups.
The indicated viscosities were determined by means of rotational viscometry according to DIN 53019 at a shear rate of 401/s using a rotational viscometer from Anton Paar Germany GmbH, Ostfildern, Germany.
The mean particle size (number average) of the polyurethane dispersions was determined by means of laser correlation spectroscopy (instrument: Malvern Zetasizer 1000, Malvern Inst. Limited, London, UK) after dilution with deionized water.
The zeta potential was measured by diluting 1 drop of the sample with 20 ml of demineralized water and homogenizing by stirring. The zeta potential was subsequently determined in a Malvern nanosizer ZS90 "(Malvern Instruments, Herrenberg, Germany) at 23 ℃.
The acid number of the respective dispersion was determined in accordance with DIN EN ISO2114: 2002-06. Instead of a mixture of toluene and ethanol as described in DIN EN ISO2114:2002-06, a mixture of acetone and ethanol (2: 1 by weight) was used as solvent. The unit of acid number is mg KOH/g of analytical sample.
Ymer N120 (CAS number: 131483-27-7, linear, trimethylolpropane-initiated polyethylene glycol monomethyl ether, OH number 100. sup. 120 mg KOH/g) was obtained from Perstorp holding AB, Malm ribbon, Sweden.
Polyester 1 OH-functional polyester prepared from 3039 g of adipic acid, 4041 g of isophthalic acid, 267 g of 1, 2-propanediol, 4773 g of neopentyl glycol and 1419 g of trimethylolpropane (OH number: 181 mg KOH/g, acid number <3 mg KOH/g)
Other chemicals were purchased from Sigma-Aldrich Chemie GmbH, Munich, Germany, unless otherwise specified.
2.1 preparation of uretdione prepolymer Dispersion A (according to the invention)
To 1000 g (4.50 mol) of isophorone diisocyanate (IPDI) were added 10 g (1%) of triisodecyl phosphite and 20 g (2%) of 4-Dimethylaminopyridine (DMAP) as catalyst at room temperature under dry nitrogen with stirring. After 20 hours, the reaction mixture having an NCO content of 28.7% (corresponding to an oligomerization degree of 21.8%) was freed of volatile constituents by means of a thin-film evaporator without prior addition of catalyst poison at a temperature of 160 ℃ and a pressure of 0.3 mbar.
This gives pale yellow uretdiones having a free NCO group content of 17.0%, a monomeric IPDI content of 0.4% and a viscosity of more than 200,000 mPas (23 ℃ C.) (to DIN EN ISO 3219: 1994-10).
149.0 g of this IPDI uretdione obtained are dissolved in 580 g of acetone at 50 ℃ in a standard stirring apparatus. 64.6 g of YMR N120 and 0.53 g of tin neodecanoate are added and the mixture is stirred under reflux at atmospheric pressure until an NCO content of 2.5% is reached. 213.20 g of polyester 1 were then added and the mixture was stirred at reflux at atmospheric pressure until the NCO content had fallen below 0.5%. The mixture was then dispersed by the addition of 213.2 grams of water. The solvent was removed by distillation in vacuo; the solids content is adjusted by adding water.
The resulting white dispersion had the following properties:
the solid content is 37%
Average particle size (LCS): 107 nm
Viscosity (viscometer, 23 ℃ C.): 118 mPas
pH (23℃): 5.3
Acid value of 0.9 mg KOH/g
Zeta potential of-16.4 mV.
3.0 testing of the coating:
a clear coat was prepared from the following composition:
100 weight percent (20 grams) of polyurethane prepolymer dispersion a (or comparative) was mixed with a catalyst solution of:
6% by weight (1.2 g) of a solution consisting of 0.12 g of Cat 1 (DBU) and 1.08 g of water
3% by weight (0.6 g) of a solution having 0.12 g of Cat 2 (Polycat SA2LE) and 0.48 g of water
5% by weight (1.0 g) of a solution consisting of 0.1 g of lithium 1,2, 4-triazole and 1.1 g of water
6% by weight (1.2 g) of a solution consisting of 0.12 g of sodium 1,2, 4-triazole and 1.08 g of water;
2.5% by weight (0.5 g) of a solution consisting of 0.12 g of sodium 1,2, 3-triazole and 0.38 g of water;
2.7% by weight (0.54 g) of a solution consisting of 0.12 g of potassium 1,2, 3-triazolate and 0.42 g of water;
2.4% by weight (0.48 g) of a solution consisting of 0.12 g of rubidium 1,2, 3-triazolate and 0.36 g of water;
2.3% by weight (0.46 g) of a solution consisting of 0.12 g of cesium 1,2, 3-triazole and 0.34 g of water;
4.5% by weight (0.91 g) of a solution having 0.12 g of sodium benzotriazole and 0.79 g of water.
The mixture was applied to the glass or web using a coating blade in a layer thickness of 150-180 μm (wet). The panels were dried at room temperature for 5 minutes and then baked at various temperatures for 30 minutes. The resulting films were evaluated for pendulum hardness, water resistance and solvent resistance at 23 ℃ at 50% relative humidity and IR spectra were recorded. Oscillation measurements are also taken if possible.
The following table shows the coating properties of the corresponding films:
Figure 214197DEST_PATH_IMAGE006
Figure 378462DEST_PATH_IMAGE007

Claims (32)

1. an aqueous curable composition comprising or consisting of
A) At least one uretdione prepolymer comprising at least one uretdione group and being passable through
A1) At least one uretdione polyisocyanate having an isocyanate functionality of at least 2.0, whereby the uretdione polyisocyanate is obtained from at least one aliphatic polyisocyanate,
and
A2) at least one compound comprising at least one Zerewitinoff-active group, and
A3) at least one reactant comprising at least one Zerewitinoff-active group and being different from A2 or being H2O，
Preferably in the presence of at least one catalyst, to obtain a uretdione prepolymer;
wherein the prepolymer has an acid number of at most 4 mg KOH/g, preferably determined in the form of a 37% by weight aqueous dispersion according to DIN EN ISO2114: 2002-06; and
B) optionally, at least one compound comprising at least one Zerewitinoff-active group; and
C) at least one azole-compound.
2. The aqueous curable composition of claim 1, characterized in that
In a first step, the at least one uretdione polyisocyanate a1 is reacted with the at least one compound a2, preferably in the presence of a catalyst, wherein the intermediate product obtained after the first step preferably has an isocyanate content of 0.5 to 10 wt.%, preferably 1 to 6 wt.%, more preferably 2 to 4 wt.%, measured according to DIN EN ISO 11909: 2007-05;
and reacting the polymer obtained in the first step with the at least one reactant a3 in a second step.
3. The aqueous curable composition of claim 1, characterized in that
The components A1 to A3 are reacted in a one-step process, preferably in the presence of a catalyst.
4. The aqueous curable composition of claim 1, characterized in that
In a first step, the at least one uretdione polyisocyanate a1 is reacted with the at least one reactant A3, and in a second step, the polymer obtained in the first step is reacted with the at least one compound a2, preferably in the presence of a catalyst.
5. The aqueous curable composition according to claim 1 characterized in that the uretdione prepolymer is a non-ionic prepolymer.
6. The aqueous curable composition according to claim 1, characterized in that the uretdione prepolymer exhibits a zeta potential of at least-20 mV.
7. According toThe aqueous curable composition of claim 1 wherein the uretdione prepolymer a comprises at least one of O- (CH)2CH2O)n-R moiety, wherein R is a hydrogen atom or (C)1-C4) -alkyl and n is a number from 3 to 100.
8. The aqueous curable composition according to claim 1, characterized in that the uretdione polyisocyanate a1 is obtained from at least one cycloaliphatic polyisocyanate.
9. The aqueous curable composition according to claim 1, characterized in that the uretdione polyisocyanate a1 is obtained from isophorone diisocyanate (IPDI), 1, 6-hexamethylene diisocyanate or a mixture thereof.
10. The aqueous curable composition according to claim 1, characterized in that the uretdione polyisocyanate a1 is prepared from at least 20 mol% of isophorone diisocyanate (IPDI) based on the total amount of polyisocyanates used.
11. The aqueous curable composition according to claim 1, characterized in that the uretdione polyisocyanate A1 is prepared from isophorone diisocyanate as the only polyisocyanate used.
12. The aqueous curable composition according to claim 1, characterized in that the uretdione polyisocyanate a1 contains 1 to 10 uretdione moieties.
13. The aqueous curable composition according to claim 1, characterized in that compound a2 is at least one polyol, preferably at least one polyalkoxy ether derivative comprising at least two-OH groups, which are present on two different non-adjacent atoms of the molecule; and more preferably selected from compounds of formula (I):
Figure 565136DEST_PATH_IMAGE001
it is characterized in that
X is H or alkyl, preferably H or C1-20-alkyl, more preferably H or C2-10-an alkyl group;
r is C1-4An alkylene group;
p is an integer from 2 to 50;
in each unit p
n is independently 0 or 1 and
m is independently 0 or 1,
provided that at least one of n or m in each unit p is 1
Which is preferably characterized in that
X is H, methyl, ethyl or propyl, preferably ethyl;
p is an integer from 5 to 25;
in each unit p
n is independently 0 or 1 and
m is independently 0 or 1,
provided that at least one of n or m in each unit p is 1 and that the total amount of n is ≧ m, preferably the total amount of n is at least 2 m, more preferably the total amount of n is at least 3 m, most preferably only n is present.
14. The aqueous curable composition according to claim 1, characterized in that compound A3 is selected from at least one polyol different from a2, preferably from polyester polyols, polyether polyols, polyurethane polyols, polyacrylate polyols, polymethacrylate polyols, polycarbonate polyols or mixtures thereof, A3 is preferably selected from polyester polyols, polyether polyols, polycarbonate polyols, polyurethane polyols, polyacrylate polyols, polymethacrylate polyols, C having at least two hydroxyl groups2-C10-hydrocarbons or mixtures thereof, a3 being most preferably polyester polyols.
15. The aqueous curable composition according to claim 1, characterized in that the compound a1 is used in an amount of 3.0 to 50.0 wt. -%, based on the total weight of compound a1 to A3.
16. The aqueous curable composition according to claim 1, characterized in that the compound a2 is used in an amount of 50 to 97% by weight, based on the total weight of compounds a1 to A3.
17. The aqueous curable composition of claim 1, characterized in that the weight ratio of a1 to a2 is from 1: 1 to 1: 32.3.
18. The aqueous curable composition according to claim 1, characterized in that the uretdione prepolymer is a dispersed uretdione prepolymer, preferably in that the uretdione prepolymer is suspended in an aqueous liquid.
19. The aqueous curable composition according to claim 1, characterized in that the uretdione prepolymer a is contained in a total amount of 3 to 40 wt. -%, based on the total weight of the composition.
20. The aqueous curable composition according to claim 1, characterized in that the azole compound C is selected from at least one triazole compound of formula (III) or a salt thereof and formula (IV) or a salt thereof
Figure 747856DEST_PATH_IMAGE002
It is characterized in that
R1、R2、R3And R4Independently selected from a hydrogen atom, a halogen atom, a nitro group, a saturated or unsaturated aliphatic or cycloaliphatic radical, an optionally substituted aromatic radical comprising up to 20 carbon atoms and optionally up to 3 heteroatoms selected from oxygen, sulfur, nitrogen, an optionally substituted araliphatic radical comprising up to 20 carbon atoms and optionally up to 3 heteroatoms selected from oxygen, sulfur, nitrogen,
and R of formula (IV) is3And R4With 1,2, 3-triazole pentazoleThe carbon atoms of the membered rings together form a fused ring having 3 to 6 carbon atoms.
21. The aqueous curable composition according to claim 20, characterized in that the azole compound C is selected from the group consisting of alkali metal-1, 2, 4-triazole salts, alkali metal-1, 2, 3-triazole salts, alkali metal-benzotriazole salts, alkaline earth metal-1, 2, 4-triazole salts, alkaline earth metal-1, 2, 3-triazole salts, alkaline earth metal-benzotriazole salts.
22. The aqueous curable composition according to claim 1, characterized in that the at least one compound B comprising at least one Zerewitinoff-active group is selected from polyester polyols, polyether polyols, polyurethane polyols, polyacrylate polyols, polymethacrylate polyols or polycarbonate polyols and mixtures thereof.
23. The aqueous curable composition according to claim 1, characterized in that the uretdione prepolymer A is contained in an amount of 1 to 50% by weight and
the at least one compound B comprising at least one Zerewitinoff-active group is contained in an amount of from 0 to 80% by weight and
the triazole compound C is contained in an amount of 0.1 to 10 wt%, based on the total weight of the composition, respectively.
24. The aqueous curable composition according to claim 1, characterized in that the composition comprises water in an amount of from 10 to 85 wt. -%, based on the total weight of the composition.
25. The aqueous curable composition according to claim 1, characterized in that the pH value at 20 ℃ is from pH 5 to pH 13.
26. A method for curing a liquid composition on a substrate comprising
a) Applying an aqueous curable composition according to any one of claims 1 to 25 on a substrate; and
b) exposing the deposited aqueous curable composition to a temperature of 60 ℃ to 160 ℃ to cure the deposited cured composition.
27. The method according to claim 26, wherein the deposited aqueous curable composition is exposed to a temperature of from 60 ℃ to 120 ℃ to cure the deposited cured composition.
28. The method according to claim 26, wherein the deposited curable composition is exposed to said temperature for a time of from 25 to 40 minutes to cure the deposited curable composition.
29. The method according to claim 26, wherein the deposited aqueous curable composition coalesces to form a coating.
30. The method according to claim 26, wherein the cured aqueous curable composition forms a solid on the substrate.
31. A cured article obtainable by the method of any one of claims 26 to 30.
32. Use of a composition according to any one of claims 1 to 25 for coatings, adhesives and/or sealants.
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US15/933,487 US20190292305A1 (en) 2018-03-23 2018-03-23 Uretdione based polyurethane compositions
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