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CN101445586A - Polyurethane compounds containing uretdione groups and hardenable at low temperature and also containing adhesion-improving resins - Google Patents

Polyurethane compounds containing uretdione groups and hardenable at low temperature and also containing adhesion-improving resins Download PDF

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Publication number
CN101445586A
CN101445586A CNA2008101787428A CN200810178742A CN101445586A CN 101445586 A CN101445586 A CN 101445586A CN A2008101787428 A CNA2008101787428 A CN A2008101787428A CN 200810178742 A CN200810178742 A CN 200810178742A CN 101445586 A CN101445586 A CN 101445586A
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acid
polyurethane composition
glycol
hydroxide
ammonium
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Inventor
P·格雷克纳
V·维斯
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Evonik Operations GmbH
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Evonik Degussa GmbH
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    • 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
    • C09D5/03—Powdery paints
    • 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
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1875—Catalysts containing secondary or tertiary amines or salts thereof containing ammonium salts or mixtures of secondary of tertiary amines and 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
    • C08G18/28—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
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/68—Unsaturated polyesters
    • C08G18/683—Unsaturated polyesters containing cyclic groups
    • C08G18/686—Unsaturated polyesters containing cyclic groups containing cycloaliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • C08G2150/00—Compositions for coatings
    • C08G2150/20—Compositions for powder coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to polyurethane compounds, which contain uretdione groups and are hardenable at low temperature and also contain adhesion-improving resins, in particular for polyurethane powder coating and adhesive compounds, which can be hardened at low temperature, to a method for the production thereof, and to the use thereof.

Description

Low-temperature curable and the polyurethane composition that contains uretdione groups that comprises adhesion-improving resins
Technical field
The present invention relates to comprise the polyurethane composition of uretdione (Uretdion) group, it can solidify at low temperatures, and comprises adhesion-improving resins, is used for solidified polyurethane powder paint vehicle and binder composition at low temperatures especially; Also relate to Its Preparation Method And Use.
Background technology
At room temperature be solid outside or enclose inside type polyisocyanates for urethane (PU) the powder paint vehicle and the binder composition of thermally cross-linkable be valuable linking agent.
DE-OS 30 30 539 and DE-OS 30 30 572 have described the method that is used to prepare the polyaddition compounds that comprises uretdione groups, and its terminal isocyanate group group is irreversibly by monohydroxy-alcohol or monoamine sealing (blockieren).Concrete defective is that the chain end-blocking component of linking agent causes the low network density (Networkdicht) in the PUR powder paint vehicle and causes the solvent resistance of moderate thus.
The theme of EP 669 353 is the hydroxy-end capped polyaddition compounds that comprises uretdione groups.Because its functionality is 2, it demonstrates the solvent resistance of raising.Based on these general character of powder paints feed composition that comprise the polyisocyanates of uretdione groups is that in curing reaction, it does not emit any volatile compound.But storing temperature is in high level, is at least 180 ℃.
Some catalyzer reduces the activation energy that is used for separating isocyanate dimer group significantly, and therefore, when use comprised the solidifying agent of uretdione groups, the solidification value of powder paint vehicle or binder composition can reduce significantly.This is favourable, because this has saved energy and has made that applying heat-sensitive substrate material with the powder paint vehicle becomes possibility.Because low solidification value, the melt viscosity of the paint vehicle preparation that is applied is higher.This has caused the surface spots of homogeneity question and powder paint vehicle film.And, because high melt viscosity, often observe the wettability of the substrate surface that reduces greatly, it is presented at the reduction and the weakening of base material bounding force more particularly of the numerical value of mechanical data.As described in the DE 10 2,004 020 451, (part) crystalline polymer that comprises hydroxyl by adding, flow problem (Verlaufsproblem) and surface spots can be eliminated, but this can not improve the base material wettability, and therefore the base material bounding force remains a problem.
Summary of the invention
Therefore, the objective of the invention is to obtain comprising the hyperergy polyurethane composition of uretdione groups, these compositions even under extremely low temperature, can also solidify, and be particularly suited for preparing the powder paint vehicle coating of the stable and Weather-stable of light, and have the numerical value aspect the base material bounding force can with correspondingly under comparatively high temps those of solidified powder paint vehicle preparation compare.
Find surprisingly, in comprising the low-temperature curing system of uretdione groups, adding or do not adding under the condition of (part) crystalline polymer that comprises oh group, improved the bounding force of base material wettability and this thus powder paint vehicle preparation greatly based on the use of the specific binder resin of unsaturated polyester, and the not any side effect on resistance properties.
Under normal circumstances (DBTL catalysis), conventional paint vehicle that contains uretdione groups and binder composition only can solidify under 180 ℃ or above temperature, prepare the coating that usually base material is had fabulous bounding force, the example of base material is not pretreated steel.Under the help of low-temperature curing composition of the present invention, solidification value at 100-160 ℃, can not only save energy and set time, can also apply or bonding many temperature sensitive base materials that under 180 ℃, can demonstrate unfavorable jaundice, decomposition and/or embrittlement phenomenon.Except that metal, glass, timber, leather, plastics and MDF plate, some aluminium substrate is intended for this.Under the situation of aluminium substrate, too high temperature load causes the unfavorable change on crystalline structure sometimes and therefore loses required mechanical property.
Theme of the present invention is solid, the hyperergy polyurethane composition that comprises uretdione groups, and it has fusing point more than 40 ℃, fabulous base material wettability and fabulous bounding force, and said composition comprises necessarily:
A) at least a solidifying agent, it comprises uretdione groups and is based on aromatics, aliphatic series, fat (ring) family and/or alicyclic polyisocyanates and hydroxy-containing compounds, and has less than the free NCO content of 5% weight and the uretdione groups content of 1%-18% weight; Based on total preparation, the amount of described solidifying agent is between 15% and 45% weight; With
B) at least a catalyzer, this catalyzer
1. has formula [XR 1R 2R 3R 4] +[R 5COO] -, X is N or P, wherein R 1To R 4Simultaneously or be alkyl, aryl, aralkyl, heteroaryl or alkoxy-alkyl group independently of one another with 1-18 carbon atom, in each case, line style or branching, not bridging or with other R 1To R 4The group bridging, forming ring, dicyclo or three rings, described bridge formation atom except carbon atom can also be heteroatoms and, for R 1To R 4Each group, can additionally have one or more alcohol, amino, ester, ketone, sulfo-, carbamate, urea, allophanate groups, two key, triple bond or halogen atom, and a R 5Be alkyl, aryl, aralkyl, heteroaryl or alkoxy-alkyl group with 1-18 carbon atom, its be line style or branching, and additionally can have one or more alcohol, amino, ester, ketone, sulfo-, acid, carbamate, urea, allophanate groups, two key, triple bond or a halogen atom
2. has formula [XR 1R 2R 3R 4] +[R 5] -, X is N or P, wherein R 1To R 4Simultaneously or be alkyl, aryl, aralkyl, heteroaryl or alkoxy-alkyl group independently of one another with 1-18 carbon atom, in each case, line style or branching, not bridging or with other R 1To R 4The group bridging, forming ring, dicyclo or three rings, the atom of described bridging except carbon can also be heteroatoms and, for R 1To R 4Each group, can additionally have one or more alcohol, amino, ester, ketone, sulfo-, acid, carbamate, urea, allophanate groups, two key, triple bond or halogen atom, and a R 5Be OH or F,
3. has formula M (OR 1) n(OR 2) m(OR 3) o(OR 4) p(OR 5) q(OR 6) r, wherein M be the metal of any nominal price oxidation state and equal n+m+o+p+q+r's and, m, o, p, q, r are 0 to 6 integers, and n+m+o+p+q+r sum=1 is to 6, radicals R 1To R 6Simultaneously or be hydrogen or alkyl independently of one another with 1-8 carbon atom, aryl, aralkyl, heteroaryl or alkoxy-alkyl group, and, in each case, described group can be line style or branching, not bridging or with other group bridging, to form ring, dicyclo or three rings, and can also be heteroatoms outside the described bridge formation atom de-carbon, additionally can have one or more alcohol, amino, ester, ketone, sulfo-, acid, carbamate, urea, allophanate groups, two keys, triple bond or halogen atom
These the group 1-3 catalyzer individually or with mixture exist and
C) at least a undersaturated, amorphous polyester, it comprises hydroxyl and carboxylic group and comprises at least a α necessarily, and β-unsaturated dicarboxylic acid component and alkoxide component, described alkoxide component are by isomeric compound 3,8-two (methylol) three ring [5.2.1.0 2,6] decane, 4,8-two (methylol) three ring [5.2.1.0 2,6] decane and 5,8-two (methylol) three ring [5.2.1.0 2,6] the tristane dimethanol mixture of decane forms,
Every kind of isomer can exist with the content of 20%-40% weight in described mixture, and the summation of three kinds of isomer is 90%-100% weight,
Exist to be not less than 5% weight in the alkoxide component of polyester with described mixture, have between 1 and the OH number of 100mg KOH/ gram and between 1 and the COOH number of 75mg KOH/ gram, the OH number is to the ratio of acid number always〉1; Based on total preparation, the weight content of described mixture is 1%-12%;
D) randomly, at least a have reactive compound to acid groups;
E) randomly, the acid of at least a monomer or polymer form;
F) randomly, at least a amorphous, hydroxyl or contain amino polymkeric substance, it has between 20 and the amine content that maybe may compare of the OH number of 500mg KOH/ gram;
G) at least a (part) crystalline hydroxyl polymer-containing, it has between 10 and the OH number of 500mgKOH/ gram; Based on total preparation, the weight content of described polymkeric substance is 1%-35%;
H) randomly, auxiliary and additive and/or other catalyzer;
The content of catalyzer B wherein) is the 0.001%-5% weight of total preparation, and component A) to H) summation be 100% weight.
Another theme of the present invention is to be used to prepare the method for polyurethane composition.
Another theme of the present invention is powder paints feed composition and powder adhesive composition, and polyurethane composition of the present invention is used to prepare in metal, plastics, glass, timber or leather substrate or other temperature-sensitive suprabasil powder paint vehicle coating and is used to prepare purposes in metal, plastics, glass, timber or leather substrate or the suprabasil powder adhesives coating of other temperature-sensitive.
Equally, theme of the present invention is to be used for metal, is used in particular for the powder paint compositions of body of a motor car, motorcycle and bike, building slab and home appliances and is used for the powder paint compositions of timber, glass, leather and plastics.
And so the goods that apply are parts of the present invention.
The polyisocyanates that comprises uretdione groups is known, and at for example US4,476,054, US 4,912,210, US 4,929,724 and EP 0 417 603 in describe.J.Prakt.Chem.336 (1994) 185-200 provide the summary that the isocyanic ester dimerization is turned to the industrial methods involving of uretdione.Isocyanic ester to the conversion of uretdione usually at soluble dimerization catalyzer, for example, the existence of dialkyl amino yl pyridines, trialkyl phosphine, phosphoryl triamide or imidazoles takes place down.This reaction is randomly carried out in solvent, but preferred under the situation that does not have solvent, when reaching required transformation efficiency, comes termination reaction by adding catalyzer poison.By short-path distillation isolate excess monomer isocyanic ester thereafter.If catalyzer is enough volatile, in the monomer separation process, reaction mixture can not contain described catalyzer.In this case, need not add catalyzer poison.Substantially, the isocyanic ester of wide region is applicable to the preparation of the polyisocyanates that comprises uretdione groups.According to the present invention preferably, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), two isocyanato-dicyclohexyl methyl hydride (H 12MDI), 2-methylpentane vulcabond (MPDI), 2,2,4-trimethyl hexamethylene diisocyanate/2,4,4-trimethyl hexamethylene diisocyanate (TMDI), norbornene alkyl diisocyanate (NBDI), methylenediphenyl diisocyanates (MDI), Tolylamine vulcabond (TDI) and tetramethyl-eylylene diisocyanate (TMXDI).More particularly preferably be IPDI and HDI.
These polyisocyanates with uretdione groups are to the solidifying agent A that comprises uretdione groups) conversion, relate to free NCO group and hydroxyl monomer or polymkeric substance, described polymkeric substance is polyester for example, polythioether, polyethers, polycaprolactam, polyepoxide, polyesteramide, urethane, or low-molecular-weight binary, ternary and/or tetravalent alcohol as chain extension agent and, randomly, monoamine and/or monohydroxy-alcohol are as the reaction of chain terminator, and (EP 669 353 by extensive description, EP 669 354, DE 30 30 572, EP 639 598 or EP 803 524).The polyester that preferably has the molecular-weight average of the OH number of 30-150mg KOH/g and 500-6000g/mol, and low molecular weight diol.The solidifying agent A that preferably comprises uretdione groups) has uretdione groups content less than the NCO content of 5% weight and 1%-18% weight (as C 2N 2O 2Calculate molecular weight 84).Remove uretdione groups, solidifying agent A) can also comprise isocyanuric acid ester, biuret, allophanate, carbamate and/or urea structure.
The catalyst B of necessity of the present invention) satisfy:
1. has formula [XR 1R 2R 3R 4] +[R 5COO] -, X is N or P, wherein R 1To R 4Simultaneously or be alkyl, aryl, aralkyl, heteroaryl or alkoxy-alkyl group independently of one another with 1-18 carbon atom, in each case, line style or branching, not bridging or with other R 1To R 4The group bridging, with the atom that forms ring, dicyclo or three rings and described bridging except carbon can also be heteroatoms and, for R 1To R 4Each group, can additionally have one or more alcohol, amino, ester, ketone, sulfo-, carbamate, urea, allophanate groups, two key, triple bond or halogen atom, and a R 5Be alkyl, aryl, aralkyl, heteroaryl or alkoxy-alkyl group with 1-18 carbon atom, its be line style or branching, and additionally can have one or more alcohol, amino, ester, ketone, sulfo-, acid, carbamate, urea, allophanate groups, two key, triple bond or a halogen atom
2. has formula [XR 1R 2R 3R 4] +[R 5] -, X is N or P, wherein R 1To R 4Simultaneously or be alkyl, aryl, aralkyl, heteroaryl or alkoxy-alkyl group independently of one another with 1-18 carbon atom, in each case, line style or branching, not bridging or with other R 1To R 4The group bridging, with the atom that forms ring, dicyclo or three rings and described bridging except carbon can also be heteroatoms and, for R 1To R 4Each group, can additionally have one or more alcohol, amino, ester, ketone, sulfo-, acid, carbamate, urea, allophanate groups, two key, triple bond or halogen atom, and a R 5Be OH or F, perhaps
3. has formula M (OR 1) n(OR 2) m(OR 3) o(OR 4) p(OR 5) q(OR 6) r, wherein M be the metal of any nominal price oxidation state and equal n+m+o+p+q+r's and, m, o, p, q and r are 0 to 6 integers, and n+m+o+p+q+r sum=1 is to 6, radicals R 1To R 6Simultaneously or be hydrogen or alkyl, aryl, aralkyl, heteroaryl or alkoxy-alkyl group independently of one another with 1-8 carbon atom, and, in each case, described group can be line style or branching, not bridging or with other group bridging, forming ring, dicyclo or three rings, and can also be heteroatoms outside the atom de-carbon of bridging and additionally can have one or more alcohol, amino, ester, ketone, sulfo-, acid, carbamate, urea, allophanate groups, two key, triple bond or halogen atom.
The example of this kind catalyzer in above-mentioned 1. parts is the formic acid tetramethyl-ammonium, the acetate tetramethyl-ammonium, the propionic acid tetramethyl-ammonium, the butyric acid tetramethyl-ammonium, the phenylformic acid tetramethyl-ammonium, the formic acid tetraethyl ammonium, the acetate tetraethyl ammonium, the propionic acid tetraethyl ammonium, the butyric acid tetraethyl ammonium, the phenylformic acid tetraethyl ammonium, the formic acid tetrapropyl ammonium, the acetate tetrapropyl ammonium, the propionic acid tetrapropyl ammonium, the butyric acid tetrapropyl ammonium, the phenylformic acid tetrapropyl ammonium, the formic acid TBuA, the tetrabutylphosphoniuacetate acetate ammonium, the propionic acid TBuA, the butyric acid TBuA, the phenylformic acid TBuA, the acetate 4-butyl-phosphonium, the formic acid 4-butyl-phosphonium, acetate Yi base triphenyl phosphonium, benzotriazole 4-butyl-phosphonium (Tetrabutylphosphoniumbenzotriazolat), phenol tetraphenylphosphoniphenolate and capric acid three hexyl Shi Si Wan Ji Phosphonium.
The example of this kind catalyzer in above-mentioned 2. parts is the hydroxide methyltributylammoni,m, hydroxide methyl triethyl ammonium, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium, hydroxide four pentyl ammonium, the hydroxide tetrahexyl ammonium, hydroxide four octyl group ammoniums, hydroxide four decyl ammoniums, hydroxide tetradecyl three hexyl ammoniums, hydroxide four (octadecyl) ammonium, the hydroxide benzyltrimethylammon.um, hydroxide benzyl triethyl ammonium ammonium, hydroxide trimethylphenyl ammonium, hydroxide triethyl ammonium methyl, hydroxide trimethyl-ethylene base ammonium, fluoridize tetramethyl-ammonium, fluoridize tetraethyl ammonium, tetrabutylammonium, fluoridize four octyl group ammoniums, fluoridize benzyltrimethylammon.um, hydroxide 4-butyl-phosphonium and fluoridize 4-butyl-phosphonium.
The example of this kind catalyzer in above-mentioned 3. parts is lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, hydrated barta, aluminium hydroxide, zinc hydroxide, lithium methoxide, sodium methylate, potassium methylate, magnesium methylate, calcium methylate, barium methylate, lithium ethoxide, sodium ethylate, potassium ethylate, magnesium ethylate, calcium ethylate, barium ethylate, lithium propoxide, sodium propylate, potassium propylate, magnesium propylate, calcium propylate, propyl alcohol barium, the Virahol lithium, sodium isopropylate, potassium isopropoxide, magnesium isopropoxide, calcium isopropoxide, barium isopropylate, 1-butanols lithium, the 1-sodium butylate, 1-butanols potassium, 1-butanols magnesium, the 1-calcium butoxide, 1-butanols barium, 2-butanols lithium, the 2-sodium butylate, 2-butanols potassium, 2-butanols magnesium, the 2-calcium butoxide, 2-butanols barium, the isobutyl lithium alkoxide, the isobutyl sodium alkoxide, the isobutyl potassium alcoholate, the isobutyl magnesium alkoxide, isopropylcarbinol calcium, isopropylcarbinol barium, trimethyl carbinol lithium, sodium tert-butoxide, potassium tert.-butoxide, tert-butyl alcohol magnesium, calcium tert-butoxide, trimethyl carbinol barium, the phenol lithium, sodium phenylate, potassium phenylate, phenol magnesium, calcium phenylate and barium phenolate.
In the nature of things, can also use this kind mixture of catalysts.In polyurethane composition, based on total preparation, described catalyzer is with 0.001%-5% weight, and the amount of preferred 0.01%-3% weight exists.Described catalyzer can comprise crystal water, in this case, when calculating the amount of catalyst system therefor, does not consider this water: promptly, the amount of described water is removed from calculate.Especially preferably use phenylformic acid tetraethyl ammonium and tetrabutylammonium.
A deformation program of the present invention comprises catalyst B) polymerization take place is attached to solidifying agent A) or to hydroxyl polymer-containing C) or polymkeric substance F) on.For example, the sulfo-of free alcohol, ammonium salt or amino group can with powder paint vehicle solidifying agent A) acid-, isocyanic ester-or glycidyl group or hydroxyl polymer-containing C) or F) reaction so that catalyst B) be incorporated into polymer complex.These catalyzer can also and form thus with the shell parcel and seal.
As component C) what use is at least a hydroxyl and carboxyl, undersaturated, amorphous polyester, it has between 1 and the OH number of 100mg KOH/ gram and between 1 and the COOH number of 75mg KOH/ gram, the OH number is to the ratio of acid number always〉1; Based on total preparation, described polyester has the weight content of 1%-12%.
Component C) relate to the polyester of undersaturated, amorphous, hydroxyl and carboxyl, it mainly comprises at least a α, and β-unsaturated dicarboxylic acid component and alkoxide component, described alkoxide component are by isomeric compound 3,8-two (methylol) three ring [5.2.1.0 2,6] decane, 4,8-two (methylol) three ring [5.2.1.0 2,6] decane and 5,8-two (methylol) three ring [5.2.1.0 2,6] the tristane dimethanol mixture of decane forms, every kind of isomer can exist with the 20%-40% weight content in described mixture, and the summation of three kinds of isomer is that 90%-100% weight and described mixture exist with at least 5% weight in the alkoxide component of polyester.
Described undersaturated, amorphous vibrin C) by alkoxide component and acid constituents reaction are obtained.
Used alkoxide component comprises isomeric compound 3 according to the present invention, 8-two (methylol) three ring [5.2.1.0 2,6] decane, 4,8-two (methylol) three ring [5.2.1.0 2,6] decane and 5,8-two (methylol) three ring [5.2.1.0 2,6] the tristane dimethanol mixture of decane, every kind of isomer can exist with the 20%-40% weight content in described mixture, and the summation of three kinds of isomer is a 90%-100% weight, be preferably 95%-100% weight and described mixture exists with at least 5% weight in the alkoxide component of polyester.The content of isomer of tristane dimethanol mixture can be analyzed qualitatively and determines quantitatively by GC for example, or by preparative gas chromatography (
Figure A200810178742D0016181112QIETU
GC) or the separation of HPLC and NMR thereafter spectrum and determining quantitatively.Under common actual environment, all corresponding isomer of 9 tristane dimethanol are equal suitable in the position, but because mirror symmetry, are nondescript with above-mentioned isomer, and cis-isomeride and trans-isomer(ide) also are nondescript.
Tristane dimethanol mixture can comprise in addition 10% weight at the most the tristane dimethanol other isomer and/or the trimeric and/or the higher isomer glycol of Diels-Alder (Diels-Alder) reaction product of cyclopentadiene.Preferably, 20% weight of described alkoxide component, 50% weight, 90% weight preferably, more preferably 100% weight is tristane dimethanol mixture, it especially preferably comprises three kinds of above-mentioned isomeric compounds of 95%-100% weight.
Except that tristane dimethanol mixture, described alkoxide component also comprises the glycol and/or the polyvalent alcohol of aliphatic and/or alicyclic and/or the aromatics of extra line style and/or branching.Preferred used additional alcohol is, ethylene glycol, 1,2-and/or 1, ammediol, Diethylene Glycol, dipropylene glycol, triethylene glycol, TEG, 1,2-and/or 1, the 4-butyleneglycol, 1,3-butyl ethyl propylene glycol, 1, the 3-methyl propanediol, 1, the 5-pentanediol, cyclohexanedimethanol, glycerol, hexylene glycol, neopentyl glycol, trimethylolethane, TriMethylolPropane(TMP) and/or tetramethylolmethane, and dihydroxyphenyl propane, B, C, F, norborneol glycol (norbornylene glycol), 1,4-benzyl dimethanol and-ethanol, 2,4-dimethyl-2-ethyl hexane-1, the 3-glycol.
Described undersaturated noncrystalline polyester resin C) comprise at least a α, β-unsaturated dicarboxylic acid is as its starting acid component.Preferably, described unsaturated polyester resin comprises citraconic acid, fumaric acid, methylene-succinic acid, toxilic acid and/or methylfumaric acid.
In addition, can also there be aromatics and/or aliphatic series and/or alicyclic monocarboxylic acid and/or dicarboxylic acid and/or poly carboxylic acid, for example phthalic acid, m-phthalic acid, terephthalic acid, 1,4-cyclohexane dicarboxylic acid, Succinic Acid, sebacic acid, methyl tetrahydrophthalic acid, methylhexahydrophthaacid acid, hexahydrophthalic acid, tetrahydrophthalic acid, dodecanedioic acid, hexanodioic acid, nonane diacid, different n-nonanoic acid, 2 ethyl hexanoic acid, pyromellitic acid (Pyromellitsure) and/or trimellitic acid.Those preferably, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, hexanodioic acid and/or nonane diacid.
Described acid constituents can partly or entirely be made up of acid anhydrides and/or alkyl ester, preferred methyl esters.
Usually, described alkoxide component exists with 0.5 to 2.0:1 preferred 0.8 to 1.5:1 mol ratio with respect to described acid constituents.Particularly preferably, described alkoxide component reacts with 1.0 to 1.1:1 mol ratio for described acid constituents.
Described undersaturated, amorphous polyester C) can have between 1 and 75mg KOH/g, preferably between 1 and 50, more preferably between 1 and the acid number of 35mg KOH/g, with between 1 and 100mg KOH/g, preferably between 1 and 75, more preferably between 1 and the OH number of 50mg KOH/g, the OH number is to the ratio of acid number always〉1.
Described undersaturated, amorphous polyester C)-30 to+80 ℃ certainly of Tg, preferred-20 to+50 ℃, more preferably-10 to+40 ℃ of variations.
In a preferred embodiment I, described unsaturated polyester resin C) (UP resin) is made up of alkoxide component and fumaric acid and/or toxilic acid (acid anhydride), described alkoxide component has at least 90% weight, preferred 95% weight and the more preferably isomeric compound 3 of 100% weight, 8-two (methylol) three ring [5.2.1.0 2,6] decane, 4,8-two (methylol) three ring [5.2.1.0 2,6] decane and 5,8-two (methylol) three ring [5.2.1.0 2,6] the tristane dimethanol mixture of decane.In further preferred embodiment II, described polyester C) comprise as the aforementioned starting ingredient in I, but and additionally be selected from the extra acid of adipic-or phthalic acid (acid anhydride), α, beta-unsaturated acid can change from 2:1 to 1:4 the ratio of additional acid.Preferred ratio is about 1:1 to 1:2.These polyester have 1-75mg KOH/g usually, preferred 1-50mg KOH/g, the more preferably acid number of 1-35mg KOH/g, 1-100mg KOH/g, preferred 1-75mg KOH/g, more preferably the OH number of 1-50mg KOH/g, the OH number is to the ratio of acid number always〉1, with-30 to+80 ℃, preferred-20 to+50 ℃, more preferably-10 to+40 ℃ Tg.
Described polyester C) can also comprise auxiliary and the additive that is selected from inhibitor, water and/or organic solvent, neutralizing agent, surfactant, oxygen scavenger and/or free-radical scavengers, catalyzer, photostabilizer, color brightener, photosensitizers, thixotropic agent, anti, defoamer, static inhibitor, thickening material, thermoplastic additive, dyestuff, pigment, fire retardant, internal mold release, filler and/or whipping agent.
Described polyester C) prepares with (partly) continuous or discrete esterification and condensation reaction by starting acid and initial alcohol with a step or two step modes.
Is known based on the tristane dimethanol as the vibrin of diol component, and, can be from DE 924 889, DE 953 117, and DE 22 45 110, and DE 27 21 989, and EP 114 208, and EP 934 988, and EP 1 492 834 learns.
EP 1 398 337 has described the bonding enhancement additive of being made up of undersaturated amorphous polyester.Described bonding enhancement additive and polymkeric substance one are used from water-based, solvent-laden (standard, middle and high, high solid) and/or not solvent-laden (powder and/or liquid) are heat-setting, radiation-hardenable, air dried (oxidation and physically) coated material, plaster material and/or sealing agent and tackiness agent, and as the modified resin that is applicable to priming paint, filler, base coating (Basislacke), individual layer external coating (EC) (Einschichtdecklacke), varnish, tackiness agent, sealing agent, road sign colorant, erosion shield.
Their purposes in comprising uretdione groups and powder paint vehicle that can be crosslinked at low temperatures are not described.Polymkeric substance according to EP 1 398 337 can have OH group and hydroxy-acid group, and not only OH number but also acid number can be between 1 and the value of 200mg KOH/g.Correspondingly, the polymkeric substance of describing in EP 1 398 337 can have high carboxylic functionality and low OH functionality.Under situation of the present invention, their use meetings in comprising the hyperergy polyurethane composition of uretdione groups,
1. because the existence of the acid groups of high density, reduce described preparation reactivity and
2. because low OH functionality causes noncrosslinking part (Anteil), influence resistance properties thus negatively.
Owing to this reason, in the present invention, the OH number is to the ratio of acid number always〉the 1st, essential.
At hydroxyl (part) crystalline polymer G) situation under, preferred polyester, polyethers, polyacrylic ester, urethane and/or the polycarbonate that uses OH number with 10-500 (mg KOH/g).Particularly preferably be the hydroxyl polyester of the molecular-weight average of OH number with 15-150 and 500-6000g/mol.In the nature of things, can also use this kind mixture of polymers.This (part) crystallographic component G) weight content in total preparation A-H can be preferably 2%-50% weight between 1%-95% weight.
Preferably (part) crystallization, hydroxyl polyester G) be to prepare by polycondensation.For this purpose, the acid constituents that to be made up of another kind of aliphatic or alicyclic or aromatic dicarboxylic acid or the poly carboxylic acid of the saturated linear aliphatic with 4-14 carbon atom of 80-100mol% or alicyclic dicarboxylic acid and 0-20mol% has the alkoxide component that the aliphatic series of 2-15 carbon atom or alicyclic diol or polyvalent alcohol forms with another kind by the two pure and mild 0-20mol% of the linear aliphatic with 2-15 carbon atom of 80-100mol% and reacts.So (part) crystalline hydroxyl polyester of preparation have 15-150mgKOH/g the OH number,＜acid number of 5mg KOH/g and 40-130 ℃ fusing point.
Preferably be used for preparation (part) crystalline polyester G) carboxylic acid be Succinic Acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid, dodecanedioic acid, tetrahydrophthalic acid, hexahydrophthalic acid, six hydrogen terephthalic acids, interior methylene radical tetrahydrophthalic acid, pentanedioic acid and-as can-its acid anhydrides.Suitable especially and dodecanedioic acid preferably.
Suitable polyvalent alcohol is following glycol: ethylene glycol, propane-1,2-two is pure and mild-1, the 3-glycol, 2,2-dimethylpropane-1, the 3-glycol, butane-1, the 4-glycol, pentane-1, the 5-glycol, hexane-1, the 6-glycol, 2-methylpentane-1, the 5-glycol, 2,2,4-trimethyl cyclohexane-1,6-glycol, 2,4,4-trimethyl cyclohexane-1,6-glycol, heptane-1, the 7-glycol, decane-1, the 10-glycol, dodecane-1, the 12-glycol, 9,10-octadecylene-1, the 12-glycol, octadecane-1, the 18-glycol, 2,4-dimethyl-2-propyl group heptane-1, the 3-glycol, butene-1, the 4-glycol, butine-1, the 4-glycol, Diethylene Glycol, triethylene glycol, TEG, trans-and cis-1,4 cyclohexane dimethanol, triol: glycerol, hexane-1,2, the 6-triol, 1,1,1-TriMethylolPropane(TMP) and 1,1,1-trimethylolethane, and tetrol: tetramethylolmethane.Preferably ethylene glycol, propane-1,2-two pure and mild-1,3-glycol, 2,2-dimethylpropane-1,3-glycol, butane-1,4-glycol, pentane-1,5-glycol, hexane-1,6-glycol, 2-methylpentane-1,5-glycol, heptane-1,7-glycol, decane-1,10-glycol, dodecane-1,12-glycol, 9,10-octadecylene-1,12-glycol, octadecane-1,18-glycol, butene-1,4-glycol, butine-1,4-glycol, Diethylene Glycol, triethylene glycol, TEG, trans and cis-1,4 cyclohexane dimethanol.
Must be noted that at B in this article) in activity of such catalysts in the presence of acid, reduce significantly.Contain the paint vehicle of uretdione or the popular response partner of tackiness agent solidifying agent, comprise the hydroxyl polyester.Because prepare the method for polyester, they also comprise acid groups on lesser extent sometimes.In the presence of the polyester that has this acid groups, compatibly, use the described catalyzer excessive, or add the reactive compounds that to remove acid groups with respect to described acid groups.Can use simple function and polyfunctional compound for this purpose.
In paint chemistry, Compound D is removed in reactive acid) be known.For example, epoxy compounds, carbodiimide class, hydroxyalkyl amide or 2-oxazoline class also have inorganic salt, and for example, oxyhydroxide, supercarbonate or carbonate at high temperature react with acid groups.Suitable example comprises, triglycidyl ether isocyanuric acid ester (TGIC), 828 (based on the diglycidylether of dihydroxyphenyl propane, Shell), tertiary carbonic acid glycidyl ester, the ethylhexyl glycidyl ether, butylglycidyl ether, Polypox R 16 (tetramethylolmethane four glycidyl ethers, UPPC AG), with other Polypox type that comprises the free epoxide group, beta-hydroxy alkylamide (for example, VestagonEP HA 320, Evonik Degussa GmbH), also has inferior Ben Ji bisoxazoline, 2-methyl-2-oxazoline, 2-hydroxyethyl-2-oxazoline, 2-hydroxypropyl-2-oxazoline, 5-hydroxyl amyl group-2-oxazoline, hydrated barta, yellow soda ash and lime carbonate.In the nature of things, the mixture of these materials also is fit to.Based on total preparation A) to H), these reactive compounds can be with 0.1%-10% weight when existing, and the weight content of preferred 0.5%-3% weight uses.
At E) in the acid of indication be have Bronsted acid (
Figure A200810178742D0020180502QIETU
) or Lewis acid (
Figure A200810178742D0020180511QIETU
) solid or liquid, organic or inorganic, monomeric or the polymeric of character, all substances.The example that can mention comprises: sulfuric acid, acetate, phenylformic acid, propanedioic acid, terephthalic acid have the copolyesters or the copolyamide of the acid number of 20mg KOH/g at least in addition.Based on total preparation, when existing, they are included in the weight content of 0.1%-10%.
For hydroxyl amorphous polymer F), preferred polyester, polyethers, polyacrylic ester, urethane and/or the polycarbonate that uses OH number with 20-500mg KOH/g.Particularly preferably be the hydroxyl polyester of the molecular-weight average of OH number with 20-150mg KOH/g and 500-6000g/mol.In the nature of things, can also use this kind mixture of polymers.Based on total preparation, this kind amorphous polymer can be with 1%-95% when existing, and the weight content of preferred 1%-90% uses.
As the alkoxide component that is used to prepare polyester, can there be the glycol and/or the polyvalent alcohol of aliphatic and/or alicyclic and/or aromatics line style and/or branching.The preferred tristane dimethanol that uses, ethylene glycol, 1,2-and/or 1, ammediol, Diethylene Glycol, dipropylene glycol, triethylene glycol, TEG, 1,2-and/or 1, the 4-butyleneglycol, 1,3-butyl ethyl propylene glycol, 1, the 3-methyl propanediol, 1, the 5-pentanediol, cyclohexanedimethanol, glycerol, hexylene glycol, neopentyl glycol, trimethylolethane, TriMethylolPropane(TMP) and/or tetramethylolmethane, and dihydroxyphenyl propane, B, C, F, norborneol glycol (norbornylene glycol), 1,4-benzyl dimethanol and-ethanol, 2,4-dimethyl-2-ethyl hexane-1,3-glycol.
As the acid constituents that is used to prepare polyester, can exist line style and/or branching, monocarboxylic acid and/or the dicarboxylic acid and/or the poly carboxylic acid of aliphatic and/or alicyclic and/or aromatics, for example, phthalic acid, m-phthalic acid, terephthalic acid, 1,4-cyclohexane dicarboxylic acid, Succinic Acid, sebacic acid, methyl tetrahydrophthalic acid, methylhexahydrophthaacid acid, hexahydrophthalic acid, tetrahydrophthalic acid, dodecanedioic acid, hexanodioic acid, nonane diacid, different n-nonanoic acid, 2 ethyl hexanoic acid, pyromellitic acid (
Figure A200810178742D0020180535QIETU
) and/or trimellitic acid.Those preferably, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, hexanodioic acid and/or nonane diacid.
Described acid constituents can all or part ofly be made up of acid anhydrides and/or alkyl ester, preferably is made up of methyl esters.
For polyurethane composition, can be added in auxiliary usual in paint vehicle or the tackiness agent technology and additive H with for example total amount of 0.05%-5% weight), for example, flow promotor (Verlaufsmittel), for example polysiloxane or acrylate, photostabilizer, for example sterically hindered amines, or other auxiliary as in EP 669 353, describing.When existing, can add filler and pigment, for example titanium dioxide with the amount of 50% weight of for example total at the most composition.
Randomly, can exist in known additional catalyst in the polyurethane chemistry.These mainly are the organo-metallic catalysts of the amount of 0.001%-1% weight for example, for example dibutyl tin laurate, or tertiary amine, for example 1,4-diazabicyclo [2.2.2] octane.
Based on total preparation, total amount H) can be a 0.001%-55% weight.
Be used to prepare all components of polyurethane composition of the present invention, can be in suitable device homogenizing, described suitable device is, for example, heatable kneader, but forcing machine more particularly, for example carrying out under 40-130 ℃ of temperature, ceiling temperature should be above 120-130 ℃.After mixing up hill and dale, by suitable applying, for example roller coat or spraying puts on base material with described material.By known method, for example, by electrostatic powder spraying or by the fluidized-bed electrostatic sintering, the powder that can be ready to spray applies to suitable substrates.After applying, the workpiece of heating through applying is 4 to 60 minutes under 60-220 ℃ temperature, and preferably, heating is 6 to 30 minutes under 80-150 ℃ temperature, to be cured.
Embodiment
Theme of the present invention illustrates by following examples.
Embodiment 1 component C) preparation
Starting ingredient: isomer ratio is the tristane dimethanol mixture of about 1:1:1
With hexanodioic acid and toxilic acid (mol ratio 1:1) and tristane dimethanol, under 180 ℃, in nitrogen atmosphere, with the molar ratio reaction of 1:1.05, until the OH number of acid number that reaches 27mg KOH/g and 36mg KOH/g.For this purpose, toxilic acid elder generation and tristane dimethanol esterification 1 hour add hexanodioic acid then.M n=1800g/mol, M w=4400g/mol, second-order transition temperature are 14 ℃.
Be used to prepare the embodiment of polyurethane powder paint vehicle
Table 1: component
The description of product, the manufacturer
VESTAGON EP-BF?9030 Solidifying agent A), NCO content: 12.3%, melting range: 73 to 76 ℃, Evonik Degussa GmbH, Coatings ﹠ Colorants
VESTAGON EP-BF?1321 Solidifying agent A), NCO content: 14.0%, melting range: 90 to 115 ℃, Evonik Degussa GmbH, Coatings ﹠ Colorants
TBAB Catalyst B) phenylformic acid TBuA, Aldrich
VESTAGON EP-R?4030 (part) crystallization OH polyester G), the OH number: 31mg KOH/g, melting range: 110 to 120 ℃, Evonik Degussa GmbH, Coatings ﹠ Colorants
URALAC?P?1580 Non-crystalline state OH polyester F), OH counts 85mg KOH/g, T G： 51℃，DSM
CRYLCOAT 2839-0 Non-crystalline state OH polyester F), OH number: 55mg KOH/g; Cytec
Benzoin Air release agent, Aldrich, H)
ARALDIT?PT?912 The solidifying agent (acid scavenger D) that comprises epoxide group, Huntsman
PRINTEX?60 Dyestuff level carbon black, Evonik Degussa GmbH, H)
KRONOS?2160 Titanium dioxide, KRONOS TITAN, H)
BLANC?FIXE?F Barium sulfate, Sachtleben Chemie GmbH, H)
RESIFLOW?PV?88 Flow promotor, Worlee Chemie GmbH, H)
T G: second-order transition temperature;
Table 2-1: polyurethane powder paint vehicle preparation
1 ＊V1 2 ＊V2
VESTAGON?EP-BF?9030 222 222 - -
VESTAGON?EP-BF?1321 - - 302 302
VESTAGON?EP-R?4030 85 85 73 73
CRYLCOAT?2839-0 335 335 - -
URALAC?P?1580 - - 291 291
TBAB 10 10 7 7
ARALDIT?PT?912 13 13 12 12
KRONOS?2160 300 300 - -
BLANC?FIXE?F - - 250 250
Printex?60 - - 10 10
Benzoin 5 5 5 5
RESIFLOW?PV?88 10 10 10 10
Component C according to embodiment 1) 20 - 40 -
The amount of mass content; *The non-invention of V, Comparative Examples
Table 2-2: polyurethane powder paint vehicle preparation
3 ＊V3
VESTAGON?EP-BF?9030 222 222
VESTAGON?EP-R?4030 275 275
TBAB 10 10
ARALDIT?PT?912 13 13
KRONOS?2160 300 300
Benzoin 5 5
RESIFLOW?PV?88 10 10
Component C according to embodiment 1) 60 -
General preparation explanation for powder paint vehicle 1-3 and V1-V3:
Intimate mixing is according to the powdery components of table 2 in pan mill, reaches homogenizing in the forcing machine of 130 ℃ of maximum values in temperature then.After the cooling, broken extrudate also uses rotating disk peg type pulverizer (Stiftm ü hle) to grind to＜100 μ m granular sizes, and by sifted to less than 63 μ m.Use the electrostatic powder spraying plant, the powder that so prepares is coated on the degrease iron plate at 60kV, and in the forced ventilation baking oven, toasting 30 minutes under 150 ℃ or toasting 30 minutes (film thicknesses: 70-80 μ m) down at 130 ℃.The result of test data lists in table 3-4.
Table 3: solidified 30 minutes down at 150 ℃
Embodiment Sven-Gan Eriksson cupping [mm] Fall-ball type impacts the dir/rev[inch ＊Pound] Gloss Cross cut test
1 12 >160/160 86 0
V1 9 100/80 88 0-1
2 10 >160/>160 90 0
V2 8 100/40 88 1
3 9 140/140 90 0-1
V3 7 120/100 90 1-2
Table 4: solidified 30 minutes down at 130 ℃
Embodiment Sven-Gan Eriksson cupping [mm] Fall-ball type impacts the dir/rev[inch ＊Pound] 60 ° of angles of gloss Cross cut test
1 11 160/160 89 0
V1 6 80/60 90 2
2 10 >160/160 88 0-1
V2 7 80/20 89 3-4
3 9 130/120 91 0-1
V3 7 90/30 89 4
Carry out erichsen test according to DIN 53 156;
Carry out the fall-ball type shock test according to ASTM D 2794-93;
Carry out cross cut test according to DIN EN ISO 2409, cutting spacing 2mm.

Claims (47)

1. comprise uretdione groups and solid hyperergy polyurethane composition, comprise necessarily with the fusing point more than 40 ℃:
A) at least a solidifying agent, it comprises uretdione groups and based on aromatics, aliphatic series, fat (ring) family and/or alicyclic polyisocyanates and hydroxy-containing compounds, and has less than the free NCO content of 5% weight and the uretdione groups content of 1%-18% weight; Based on total preparation, the amount of described solidifying agent is between 15% and 45% weight; With
B) at least a catalyzer, this catalyzer
1. has formula [XR 1R 2R 3R 4] +[R 5COO] -, X is N or P, wherein R 1To R 4Simultaneously or be alkyl, aryl, aralkyl, heteroaryl or alkoxy-alkyl group independently of one another with 1-18 carbon atom, in each case, line style or branching, not bridging or with other R 1To R 4The group bridging, to form ring, dicyclo or three rings, bridge formation atom can also be heteroatoms except carbon atom, and R 1To R 4Each group can have one or more alcohol, amino, ester, ketone, sulfo-, carbamate, urea, allophanate groups, two key, triple bond or halogen atom extraly, and R 5Be alkyl, aryl, aralkyl, heteroaryl or alkoxy-alkyl group with 1-18 carbon atom, its be line style or branching, and additionally can have one or more alcohol, amino, ester, ketone, sulfo-, acid, carbamate, urea, allophanate groups, two key, triple bond or a halogen atom
2. has formula [XR 1R 2R 3R 4] +[R 5] -, X is N or P, wherein R 1To R 4Simultaneously or be alkyl, aryl, aralkyl, heteroaryl or alkoxy-alkyl group independently of one another with 1-18 carbon atom, in each case, line style or branching, not bridging or with other R 1To R 4The group bridging, to form ring, dicyclo or three rings, bridge formation atom can also be heteroatoms except carbon, and R 1To R 4Each group can have one or more alcohol, amino, ester, ketone, sulfo-, acid, carbamate, urea, allophanate groups, two key, triple bond or halogen atom extraly and R5 is OH or F,
3. has formula M (OR 1) n(OR 2) m(OR 3) o(OR 4) p(OR 5) q(OR 6) r, wherein M be the metal of any nominal price oxidation state and equal n+m+o+p+q+r's and, m, o, p, q, r are 0 to 6 integers, and n+m+o+p+q+r sum=1 is to 6, radicals R 1To R 6Simultaneously or be hydrogen or alkyl independently of one another with 1-8 carbon atom, aryl, aralkyl, heteroaryl or alkoxy-alkyl group, and, in each case, described group can be line style or branching, not bridging or with other group bridging, to form ring, dicyclo or three rings, and can also heteroatoms outside the bridge formation atom de-carbon, additionally can have one or more alcohol, amino, ester, ketone, sulfo-, acid, carbamate, urea, allophanate groups, two keys, triple bond or halogen atom
These from the group 1-3 catalyzer individually or with mixture exist and
C) at least a undersaturated, amorphous polyester, it comprises hydroxyl and carboxylic group and comprises at least a α necessarily, and β-unsaturated dicarboxylic acid component and alkoxide component, described alkoxide component comprise by isomeric compound 3,8-two (methylol) three ring [5.2.1.0 2,6] decane, 4,8-two (methylol) three ring [5.2.1.0 2,6] decane and 5,8-two (methylol) three ring [5.2.1.0 2,6] the tristane dimethanol mixture of decane,
Every kind of isomer can exist with the content of 20%-40% weight in described mixture, and the summation of three kinds of isomer is 90%-100% weight,
Exist to be not less than 5% weight in the alkoxide component of polyester with described mixture, have between 1 and the OH number of 100mg KOH/ gram and between 1 and the COOH number of 75mg KOH/ gram, the OH number is to the ratio of acid number always〉1; Based on total preparation, the weight content of described polyester is 1%-12%;
D) randomly, at least a have reactive compound to acid groups;
E) randomly, the acid of at least a monomer or polymer form;
F) randomly, at least a amorphous, hydroxyl or contain amino polymkeric substance, it has between 20 and the amine content that maybe may compare of the OH number of 500mg KOH/ gram;
G) at least a (part) crystalline hydroxyl polymer-containing, it has between 10 and 500mg
The OH number of KOH/ gram; Based on total preparation, the weight content of described polymkeric substance is 1%-35%;
H) randomly, auxiliary and additive and/or other catalyzer;
The content of catalyzer B wherein) is the 0.001%-5% weight of total preparation, and component A) to H) summation be 100% weight.
2. according to the polyurethane composition of claim 1, it is characterized in that, comprise
D) at least a have reactive compound to acid groups, and based on total preparation, the weight content of described compound is 0.1%-10%; And/or
E) acid of at least a monomer or polymer form, based on total preparation, the weight content of described acid is 0.1%-10%; And/or
F) at least a amorphous, hydroxyl or contain amino polymkeric substance, it has between 20 and the amine content that maybe may compare of the OH number of 500mg KOH/ gram, and based on total preparation, the weight content of described polymkeric substance is 1-95%.
3. according to the polyurethane composition of claim 1 or 2, it is characterized in that,, comprise auxiliary and the additive and/or other the catalyzer H of 0.001%-55% weight content) based on total preparation.
4. according at least one polyurethane composition among the claim 1-3, it is characterized in that, comprise the solidifying agent A that contains uretdione groups), described solidifying agent A) based on isophorone diisocyanate independent or form of mixtures (IPDI), hexamethylene diisocyanate (HDI), two isocyanato-dicyclohexyl methyl hydride (H 12MDI), 2-methylpentane vulcabond (MPDI), 2,2,4-trimethyl hexamethylene diisocyanate/2,4,4-trimethyl hexamethylene diisocyanate (TMDI), norbornene alkyl diisocyanate (NBDI), methylenediphenyl diisocyanates (MDI), Tolylamine vulcabond (TDI) and tetramethyl-eylylene diisocyanate (TMXDI).
5. according to the polyurethane composition of claim 4, it is characterized in that, comprise the solidifying agent that contains uretdione groups based on IPDI, H12MDI and/or HDI.
6. according at least one polyurethane composition among the claim 1-5, it is characterized in that, comprise the solidifying agent A that contains uretdione groups), described solidifying agent A) based on polyester independent or form of mixtures, polythioether, polyethers, polycaprolactam, polyepoxide, polyesteramide, urethane, low-molecular-weight binary, ternary and/or tetravalent alcohol, monoamine and/or monohydroxy-alcohol.
7. according to the polyurethane composition of claim 6, it is characterized in that, comprise polyester and/or monomer dibasic alcohol.
8. according to the polyurethane composition of claim 7, it is characterized in that, comprise the polyester of the molecular-weight average of OH number with 30-150mg KOH/g and 500-6000g/mol.
9. according at least one polyurethane composition among the claim 1-8, it is characterized in that described solidifying agent A) also comprise isocyanuric acid ester, biuret, allophanate, carbamate and/or urea structure.
10. according at least one polyurethane composition among the claim 1-9, it is characterized in that, comprise and be selected from the formic acid tetramethyl-ammonium, the acetate tetramethyl-ammonium, the propionic acid tetramethyl-ammonium, the butyric acid tetramethyl-ammonium, the phenylformic acid tetramethyl-ammonium, the formic acid tetraethyl ammonium, the acetate tetraethyl ammonium, the propionic acid tetraethyl ammonium, the butyric acid tetraethyl ammonium, the phenylformic acid tetraethyl ammonium, the formic acid tetrapropyl ammonium, the acetate tetrapropyl ammonium, the propionic acid tetrapropyl ammonium, the butyric acid tetrapropyl ammonium, the phenylformic acid tetrapropyl ammonium, the formic acid TBuA, the tetrabutylphosphoniuacetate acetate ammonium, the propionic acid TBuA, the butyric acid TBuA, the phenylformic acid TBuA, the acetate 4-butyl-phosphonium, the formic acid 4-butyl-phosphonium, acetate Yi base triphenyl phosphonium, the benzotriazole 4-butyl-phosphonium, the catalyzer 1. of phenol tetraphenylphosphoniphenolate and capric acid three hexyl Shi Si Wan Ji Phosphonium.
11. according at least one polyurethane composition among the claim 1-9, it is characterized in that, comprise and be selected from the hydroxide methyltributylammoni,m, hydroxide methyl triethyl ammonium, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium, hydroxide four pentyl ammonium, the hydroxide tetrahexyl ammonium, hydroxide four octyl group ammoniums, hydroxide four decyl ammoniums, hydroxide tetradecyl three hexyl ammoniums, hydroxide four (octadecyl) ammonium, the hydroxide benzyltrimethylammon.um, hydroxide benzyl triethyl ammonium ammonium, hydroxide trimethylphenyl ammonium, hydroxide triethyl ammonium methyl, hydroxide trimethyl-ethylene base ammonium, fluoridize tetramethyl-ammonium, fluoridize tetraethyl ammonium, tetrabutylammonium, fluoridize four octyl group ammoniums, fluoridize benzyltrimethylammon.um, hydroxide 4-butyl-phosphonium and the catalyzer 2. of fluoridizing 4-butyl-phosphonium.
12. according at least one polyurethane composition among the claim 1-10, it is characterized in that, comprise and be selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, hydrated barta, aluminium hydroxide, zinc hydroxide, lithium methoxide, sodium methylate, potassium methylate, magnesium methylate, calcium methylate, barium methylate, lithium ethoxide, sodium ethylate, potassium ethylate, magnesium ethylate, calcium ethylate, barium ethylate, lithium propoxide, sodium propylate, potassium propylate, magnesium propylate, calcium propylate, propyl alcohol barium, the Virahol lithium, sodium isopropylate, potassium isopropoxide, magnesium isopropoxide, calcium isopropoxide, barium isopropylate, 1-butanols lithium, the 1-sodium butylate, 1-butanols potassium, 1-butanols magnesium, the 1-calcium butoxide, 1-butanols barium, 2-butanols lithium, the 2-sodium butylate, 2-butanols potassium, 2-butanols magnesium, the 2-calcium butoxide, 2-butanols barium, the isobutyl lithium alkoxide, the isobutyl sodium alkoxide, the isobutyl potassium alcoholate, the isobutyl magnesium alkoxide, isopropylcarbinol calcium, isopropylcarbinol barium, trimethyl carbinol lithium, sodium tert-butoxide, potassium tert.-butoxide, tert-butyl alcohol magnesium, calcium tert-butoxide, trimethyl carbinol barium, the phenol lithium, sodium phenylate, potassium phenylate, phenol magnesium, the catalyzer 3. of calcium phenylate and barium phenolate.
13. at least one polyurethane composition according among the claim 1-12 is characterized in that, described catalyzer can also and form thus with inertia shell parcel and seal.
14. at least one polyurethane composition according among the claim 1-13 is characterized in that described catalyzer is through the polymerization take place combination.
15. according at least one polyurethane composition among the claim 1-14, it is characterized in that, comprise as hydroxyl (part) crystalline polymer G) polyester, polyethers, polyacrylic ester, urethane and/or the polycarbonate of OH number with 10-500mg KOH/g.
16. the polyurethane composition according to claim 15 is characterized in that, comprises the hydroxyl polyester G of the molecular-weight average of OH number with 15-150 and 500-6000g/mol).
17. polyurethane composition according to claim 16, it is characterized in that, comprise based on Succinic Acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid, dodecanedioic acid, tetrahydrophthalic acid, hexahydrophthalic acid, six hydrogen terephthalic acids, interior methylene radical tetrahydrophthalic acid, pentanedioic acid and, if-can obtain-, the polyester G of their acid anhydrides).
18. at least one polyurethane composition according in claim 16 and 17 is characterized in that, comprises based on ethylene glycol, propane-1,2-two is pure and mild-1, the 3-glycol, 2,2-dimethylpropane-1, the 3-glycol, butane-1, the 4-glycol, pentane-1, the 5-glycol, hexane-1, the 6-glycol, 2-methylpentane-1, the 5-glycol, 2,2,4-trimethyl cyclohexane-1, the 6-glycol, 2,4,4-trimethyl cyclohexane-1, the 6-glycol, heptane-1, the 7-glycol, decane-1, the 10-glycol, dodecane-1, the 12-glycol, 9,10-octadecylene-1, the 12-glycol, octadecane-1, the 18-glycol, 2,4-dimethyl-2-propyl group heptane-1, the 3-glycol, butene-1, the 4-glycol, butine-1, the 4-glycol, Diethylene Glycol, triethylene glycol, TEG, trans-and cis-1,4 cyclohexane dimethanol, triol: glycerol, hexane-1,2, the 6-triol, 1,1,1-TriMethylolPropane(TMP) and 1,1,1-trimethylolethane, and tetrol: the polyester G of tetramethylolmethane).
19. at least one polyurethane composition according among the claim 1-18 is characterized in that, comprises as component D) epoxy compounds, carbodiimide class, hydroxyalkyl amide, subsalt and/or 2-oxazoline class.
20. at least one polyurethane composition according among the claim 1-19 is characterized in that, comprises as sour E) sulfuric acid, acetate, phenylformic acid, propanedioic acid, terephthalic acid, have the copolyesters or the copolyamide of the acid number of 20mg KOH/g at least.
21. according at least one polyurethane composition among the claim 1-20, it is characterized in that, comprise as amorphous hydroxyl polymer-containing F) polyester, polyethers, polyacrylic ester, urethane, polyethers and/or the polycarbonate of OH number with 20-500mg KOH/g.
22. according at least one polyurethane composition in the aforementioned claim, it is characterized in that, at component C) in comprise the trimeric of Diels-Alder reaction product of other isomer of the tristane dimethanol of 10% weight at the most and/or cyclopentadiene and/or higher isomer glycol.
23. at least one polyurethane composition according in the aforementioned claim is characterized in that, at component C) in, described acid constituents additionally comprises aromatics and/or aliphatic series and/or alicyclic monocarboxylic acid and/or dicarboxylic acid and/or poly carboxylic acid.
24. at least one polyurethane composition according in the aforementioned claim is characterized in that, at component C) in, described acid constituents is made up of acid anhydrides and/or alkyl ester whole or in part.
25. at least one polyurethane composition according in the aforementioned claim is characterized in that, at component C) in, described alkoxide component comprises the glycol and/or the polyvalent alcohol of aliphatic and/or alicyclic and/or the aromatics of extra line style and/or branching.
26. at least one polyurethane composition according in the aforementioned claim is characterized in that, at component C) in comprise as α the citraconic acid of β-unsaturated dicarboxylic acid, fumaric acid, methylene-succinic acid, toxilic acid and/or methylfumaric acid.
27. according at least one polyurethane composition in the aforementioned claim, it is characterized in that, at component C) in comprise phthalic acid, m-phthalic acid, terephthalic acid, 1 as extra acid, 4-cyclohexane dicarboxylic acid, Succinic Acid, sebacic acid, methyl tetrahydrophthalic acid, methylhexahydrophthaacid acid, hexahydrophthalic acid, tetrahydrophthalic acid, dodecanedioic acid, hexanodioic acid, nonane diacid, pyromellitic acid and/or trimellitic acid, their acid anhydrides and/or methyl esters, and/or different n-nonanoic acid and/or 2 ethyl hexanoic acid.
28. according at least one polyurethane composition in the aforementioned claim, it is characterized in that, at component C) in comprise ethylene glycol as extra alcohol, 1,2-and/or 1, ammediol, Diethylene Glycol, dipropylene glycol, triethylene glycol, TEG, 1,2-and/or 1, the 4-butyleneglycol, 1,3-butyl ethyl propylene glycol, 1, the 3-methyl propanediol, 1, the 5-pentanediol, cyclohexanedimethanol, glycerol, hexylene glycol, neopentyl glycol, trimethylolethane, TriMethylolPropane(TMP) and/or tetramethylolmethane, and dihydroxyphenyl propane, B, C, F, the norborneol glycol, 1,4-benzyl dimethanol and-ethanol, 2,4-dimethyl-2-ethyl hexane-1,3-glycol.
29. at least one polyurethane composition according in the aforementioned claim is characterized in that, at component C) in comprise as α the fumaric acid of beta-unsaturated acid component and/or toxilic acid (acid anhydride).
30. at least one polyurethane composition according in the aforementioned claim is characterized in that, at component C) in comprise hexanodioic acid and/or phthalic acid (acid anhydride) as extra dicarboxylic acid component.
31. at least one polyurethane composition according in the aforementioned claim is characterized in that, at component C) in to comprise mol ratio with respect to described acid constituents be 0.5 to 2.0:1 described alkoxide component.
32. at least one polyurethane composition according in the aforementioned claim is characterized in that, at component C) in to comprise mol ratio with respect to described acid constituents be 0.8 to 1.5:1 described alkoxide component.
33. at least one polyurethane composition according in the aforementioned claim is characterized in that, at component C) in to comprise mol ratio with respect to described acid constituents be 1.0 to 1.1:1 described alkoxide component.
34. at least one polyurethane composition according in the aforementioned claim is characterized in that, described polyester C) have between 1 and the acid number of 50mg KOH/g, preferably between 1 and the acid number of 35mgKOH/g.
35. at least one polyurethane composition according in the aforementioned claim is characterized in that, described polyester C) have an OH number between 1 and 75, preferably between 1 and the OH number of 50mg KOH/g.
36. be used for preparation method, by homogenizing under 40-130 ℃ of temperature according at least one the polyurethane composition of aforementioned claim 1-35.
37. powder paints feed composition, said composition comprise according at least one compound among the aforementioned claim 1-35.
38. the binder composition of powder type, said composition comprise according at least one compound among the aforementioned claim 1-35.
39. be used to prepare the powder paint vehicle that is used for metal, plastics, timber, glass, leather or other temperature-sensitive substrate or the purposes of powder adhesives coating according at least one polyurethane composition among the aforementioned claim 1-36.
40. the metal coating composition of powder type comprises necessarily according at least one polyurethane composition among the claim 1-35.
41. the wood coating composition of powder type comprises necessarily according at least one polyurethane composition among the claim 1-35.
42. the leather coating composition of powder type comprises necessarily according at least one polyurethane composition among the claim 1-35.
43. the plastic paint composition of powder type comprises necessarily according at least one polyurethane composition among the claim 1-35.
44., be used for body of a motor car, motorcycle and bike, building slab and home appliances according to the metal coating composition of claim 40.
45. through the goods that apply, these goods have according at least one polyurethane composition among the claim 1-35.
CNA2008101787428A 2007-11-27 2008-11-26 Polyurethane compounds containing uretdione groups and hardenable at low temperature and also containing adhesion-improving resins Pending CN101445586A (en)

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