WO2011110640A1 - Bei hitze härtende pulverlackzusammensetzungen, welche nach aushärtung der beschichtung zu einer matten oberfläche führen, sowie ein einfaches verfahren zur ihrer herstellung - Google Patents
Bei hitze härtende pulverlackzusammensetzungen, welche nach aushärtung der beschichtung zu einer matten oberfläche führen, sowie ein einfaches verfahren zur ihrer herstellung Download PDFInfo
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- WO2011110640A1 WO2011110640A1 PCT/EP2011/053639 EP2011053639W WO2011110640A1 WO 2011110640 A1 WO2011110640 A1 WO 2011110640A1 EP 2011053639 W EP2011053639 W EP 2011053639W WO 2011110640 A1 WO2011110640 A1 WO 2011110640A1
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- powder coating
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- RRAOOBQCQCDRKP-UHFFFAOYSA-N OCCN(CCO)C(C(CC1)CCC1C(N(CCO)CCO)=O)=O Chemical compound OCCN(CCO)C(C(CC1)CCC1C(N(CCO)CCO)=O)=O RRAOOBQCQCDRKP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/44—Amides
- C08G59/46—Amides together with other curing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C09D5/032—Powdery paints characterised by a special effect of the produced film, e.g. wrinkle, pearlescence, matt finish
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
- Y10T428/3179—Next to cellulosic
Definitions
- the invention relates to heat-curing powder coating compositions which have a matte surface after curing of the coating and to a simple process for their preparation.
- Thermosetting powder coatings do not give organic when applied
- Typical binder systems are epoxy resins with hardeners based on amines, amidines, acids, anhydrides; Carboxyl polyesters or polyacrylates with epoxy-based curing agents; Hydroxyl polyesters or polyacrylates with crosslinkers based on blocked isocyanates; Epoxy-containing polyacrylates with dicarboxylic acids as crosslinkers, carboxyl polyesters or - polyacrylates with crosslinkers based on ß-hydroxyalkylamides u. a.
- the different binder systems differ in addition to the coating properties, especially in the resistance to outdoor weathering.
- the pure binder systems usually lead to high-gloss surfaces, with a gloss level of> 80 scale divisions (DIN 67530 / ISO 2813, angle of incidence 60 °) when in a so-called one-shot process with only one reactant, e.g. Crosslinker and resin, processed and cured.
- Coating systems that give a substrate a uniform flat and matte finish are of considerable interest. The reason for this is mainly practical. Glossy surfaces require a much higher degree of cleaning than dull surfaces. In addition, it may look
- WO-A-89/06674 describes the production of satin-glossy or matt surfaces by drybending, ie physical mixtures of finished powder coatings, which are composed of different binder systems.
- EP 366 608 also proposes a process for producing powder coatings with matte surfaces. It relates to powder coatings based on
- Epoxy resins or epoxy compounds such as. B. triglycidyl isocyanurate (TGIC) with carboxyl-terminated polyester resins and mixtures of di-, tri- or tetrakis- (ß-carboxyethyl) cyclohexanones or cyclopentanones.
- TGIC triglycidyl isocyanurate
- the matte effect is attributed here to the different reactivity between the aliphatic carboxylate groups of the crosslinker and the aromatic carboxylate groups of the carboxyl-terminated polyester resin.
- Polyester resins epoxy compounds, such as. As TGIC and special reversibly blocked polyisocyanates with free carboxylate groups.
- US Pat. No. 4,801,680 (EP 322 834) describes a thermosetting powder coating which consists of a particle mixture of a carboxylate-containing polyester and a ⁇ -hydroxyalkylamide. This powder coating leads after application on a support to shiny lacquer surfaces. According to Example 2 of US Pat. No. 4,801,680, the lacquer surfaces obtained after carrying out an accelerated weathering test and using UV irradiation show no impairment of the lacquer surface.
- EP 520429 describes a resin composition of polyesters with
- the described resin composition necessarily comprises an essentially ungelled polyester A, an im
- Curing agent and an organic sulfonic acid as a catalyst are examples of Curing agent and an organic sulfonic acid as a catalyst.
- Example 2 discloses, in particular in Example 1, the compound N 1 , N 1 , N 4 , N 4 -tetrakis (2-hydroxyethyl) cyclohexane-1, 4-dicarboxamide (formula 3) mentioned there 2 has only one peak according to DSC analysis with a maximum peak at about 190 ° C.
- a cis / trans content of the compound is not mentioned Further, carboxyl group-containing polyesters which are not well defined but only by wide ranges of some Can be specified (polyester not clearly characterized and unknown on the market with this viscosity), crosslinked with this compound and with the known ß-hydroxyalkylamides, here in Example 3 called as [N 1 , N 1 , N 6 , N 6 - tetrakis ( 2-hydroxyethyl) adipamide] (obtain commonly known as VESTAGON HAA 320 or PRIMID XL 552), ie with prior art curatives and long established market products, and which are known to result in glossy surfaces of the coatings produced.
- the sheets are shown. It is not described that it is dull coatings. This is also not possible because glossy coatings are obtained with the conventional hardener.
- Hydroxyalkylamides are well known in the art so-called dry blends, d. H. it requires the separate production of two Hydroxyalkylamidpullegacke based on ß-hydroxyalkylamides plus resins (polymers) with different acid numbers, which are then fed as a dry blend of the grinding. This requires a considerable additional effort and leads to a deviation
- the object of the invention was to find a heat-curing powder coating composition which have a matte surface after curing of the coating and to find a simple process for their preparation.
- the invention relates to a powder coating composition, essentially containing
- At least one carboxylate group-containing polymer having an acid number of 5 to 350 mg KOH / g, and a glass transition temperature T g of greater than 40 ° C, and
- R 1 , R 2 independently of one another are identical or different radicals selected from the alkyl radical, cycloalkyl radical, aryl radical, aralkyl radical or alkenyl radical having 1 to 24 carbon atoms, where the radicals may also contain heteroatoms and / or functional groups,
- R 1 may also be hydrogen, and wherein R 2 is also can be;
- R 3 independently of one another identical or different radicals selected from hydrogen, alkyl radical, cycloalkyl radical, aryl radical, aralkyl radical or alkenyl radical having 1 to 24 carbon atoms, which radicals may also contain heteroatoms and / or functional groups, and where two or more radicals selected from hydrogen, alkyl radical, cycloalkyl radical, aryl radical, aralkyl radical or alkenyl radical having 1 to 24 carbon atoms, which radicals may also contain heteroatoms and / or functional groups, and where two or more
- Substituents R 3 may be linked together to form rings; wherein the ⁇ -hydroxyalkylamides are below 150 ° C in solid form; C) optional adjuvants and / or additives; wherein the ratio of ⁇ -hydroxyalkylamide groups to the
- Coatings with matte (10 - 30 units) and semi matte (30 - 50 units) surfaces measured as reflectometer values according to DIN 67530 / ISO 2813 at an angle of incidence of 60 ° can be obtained.
- the inventive Powder coating composition can be obtained on the basis of carboxylate-containing polymers and ⁇ -hydroxyalkylamides according to the invention as crosslinking agents.
- crosslinker and hardener are used equally important.
- Polyester blend or polyacrylate mixture of at least two resins with different reactivity required Polyester blend or polyacrylate mixture of at least two resins with different reactivity required.
- Carboxylate group-containing polymers A) in question As polymers it is possible to use polymers, polycondensates and polyaddition compounds. In principle, any polymer can be used which contains at least two carboxylate groups and glass transition temperature T g greater than 40 ° C. Poloxylate-containing polymers are suitable for the powder coatings according to the invention those having acid numbers of 5 - 350 mg KOH / g, preferably 15 - 150 mg KOH / g, with OH numbers ⁇ 15 mg KOH / g. Preferably, these polymers have at least two terminal carboxylate groups.
- the carboxylates containing polyesters A) are preferably polyester polycarboxylic acids which are prepared from polyols and polycarboxylic acids or derivatives thereof.
- the glass transition temperature T g of these acidic polyesters is in a range of 40 to 80 ° C, preferably 40 to 70 ° C; their acid value varies from 5 to 250 mg KOH / g, preferably from 10 to 150 mg KOH / g, preferably from 12 to 120 mg KOH / g.
- the OH numbers are below 15 mg KOH / g. They have an average molecular weight M w of from 1000 to 10000 g / mol, preferably from 1 500 to 9000 g / mol, particularly preferably from 2000 to 8000 g / mol.
- Pyromellitic acid used for the acidic polyesters.
- the following are used as examples of the following: ethylene glycol, 1,2,3- and 1,3-propanediol, 1,2-, 1,3-, 1,4- and 2,3-butanediol, 1,5-pentanediol , 3-methyl-1,5-pentanediol, neopentyl glycol, 1,12-dodecanediol, 2,2,4 (2,4,4) -trimethyl-1,6-hexanediol, trimethylolpropane, glycerol, pentaerythritol, 1, 4- Bishydroxymethylcyclohexane, cyclohexane-1, 4-diol,
- Diethylene glycol, triethylene glycol and dipropylene glycol Diethylene glycol, triethylene glycol and dipropylene glycol.
- hydroxyl-containing polyesters prepared by known methods from polycarboxylic acids and polyols can be reacted with polycarboxylic acids and / or polycarboxylic anhydrides to the polyester polycarboxylic acids.
- the preparation of the carboxylate-containing polyester resins is carried out by known processes by esterification or transesterification of di- and / or polyvalent linear or branched, aliphatic or cycloaliphatic polyols with polybasic, preferably di- or polyhydric aliphatic, cycloaliphatic or aromatic carboxylic acids or their anhydrides or their esters in Presence of an esterification or transesterification catalyst at temperatures up to about 250 ° C and towards the end under reduced pressure.
- Preferred polyols are 2,2-dimethyl-1,3-propanediol (neopentyl glycol),
- the polyol component contains a high proportion of neopentyl glycol to obtain the highest possible glass transition temperatures.
- Functionality of the preferred carboxylate group-containing polyester resins is adjusted via the ratio of di- and more than dibasic carboxylic acids.
- the polyacrylate contains carboxylic acid groups and may be a homopolymer or a copolymer.
- Monomers which can be used are acrylic acid and / or methacrylic acid, C 1 -C 40 -alkyl esters and / or cycloalkyl esters of methacrylic acid and / or acrylic acid,
- Hydroxyalkyl acrylates and / or hydroxyalkyl methacrylates glycidyl methacrylate, glycidyl acrylate, 1, 2-epoxybutyl acrylate, 1, 2-epoxybutyl methacrylate, 2,3-epoxycyclopentyl acrylate, 2,3-epoxycyclopentyl methacrylate and the analogous amides, wherein also styrene and / or its derivatives may be present.
- butyl acrylate and / or butyl methacrylate Preference is given to using butyl acrylate and / or butyl methacrylate, 2-hydroxyethyl acrylate and / or 2-hydroxyethyl methacrylate, methyl methacrylate, styrene, (meth) acrylic acid and optionally further unsaturated monomers, where at least one carboxylate group-containing monomer is used.
- Methacrylic acid having 2 to 18 carbon atoms in the (cyclo) alkyl radical.
- suitable or preferably suitable monomers are ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate,
- styrene vinyl toluene and ethyl styrene into consideration.
- acrylic and methacrylic acid which are also preferably used, as well as crotonic acid, itaconic acid, fumaric acid, maleic acid and citaconic acid.
- the polyacrylate preferably has an OH number of less than 10 mg KOH / g, an acid number of 5 to 350 mg KOH / g, preferably 20 to 300 mg KOH / g, particularly preferably from 30 to 250 mg KOH / g, a Tg of 40 to 1 10 ° C, preferably 45 to 100 ° C, an M w of 500 to 50 000 g / mol, preferably 1 000 to 30 000 g / mol, particularly preferably from 1 500 to 20 000 g / mol.
- glycidyl ethers and glycidyl esters aliphatic epoxides, diglycidyl ethers based on bisphenol A and glycidyl methacrylates.
- epoxides are triglycidyl isocyanurate (TGIC trade names, e.g., ARALDIT PT 810, Huntsman, TEPIC G, Nissan, Taida TGIC, Anhui Taida), mixtures of
- the ⁇ -hydroxyalkylamides B) can be prepared from various starting materials. The reaction of ⁇ -hydroxyalkylamines with esters of carboxylic acids is known, the latter producing the skeleton (A). Depending on the choice of the starting materials, the ⁇ -hydroxyalkylamides according to the invention can be produced in this way.
- Suitable ⁇ -hydroxyalkylamines are those which have alkyl groups with at least 2 to 10 carbon atoms in the hydrocarbon skeleton.
- the alkyl groups may be linear, branched or cyclic. Likewise, the
- Alkyl groups with heteroatoms, preferably oxygen, nitrogen substituted may also contain functional groups, preferably carbonyl groups, carboxyl groups, amino groups, amide groups, urethane groups and may carry an additional alkyl radical on the nitrogen.
- the ⁇ -hydroxyalkylamides are prepared from N-alkyl-1,2-alkanolamines and / or from N, N-bis-2-hydroxyalkylamines and esters of cyclohexanedicarboxylic acids.
- R 1 is hydrogen, methyl, ethyl, propyl,
- R is methyl
- the following compounds are used as starting materials for the preparation of ß-hydroxyalkylamides: diethanolamine (DEA), di-isopropanolamine (DIPA), di-sec-butanolamine, N-methylethanolamine, N-methyl-isopropanolamine.
- Suitable starting compounds for the substituent A in the ⁇ -hydroxyalkylamides according to the invention are 1, 2, 1, 3 and 1, 4-cyclohexanedicarboxylic acid derivatives, in particular
- the starting compounds may have any desired cis / trans content.
- the present invention particularly preferred ⁇ -hydroxyalkylamides of dialkyl-1, 4-cyclohexyldicarboxylaten, preferably from dimethyl-1, 4-cyclohexyldicarboxylat, have a trans content, based on the position of the carboxyl groups on the cyclohexyl of greater than or equal to 70 mol%, preferably greater 80 mol%, and more preferably greater than 85 mol%.
- dialkyl-1, 4-cyclohexyldicarboxylate can be used for the preparation of the preferred ß-hydroxyalkylamides having any trans content.
- the ⁇ -hydroxyalkylamides (I) according to the invention are present in solid form below 150 ° C., preferably below 170 ° C., particularly preferably below 180 ° C.
- R 2 methyl, or
- R 1 B is methyl, ethyl, propyl, or
- R 1A is methyl, ethyl, propyl and R 1B is hydrogen
- trans content of A is> 70 mol%; and wherein the ⁇ -hydroxyalkylamides are below 150 ° C in solid form.
- the present invention particularly preferred ⁇ -hydroxyalkylamide of dimethyl-1, 4-cyclohexyldicarboxylate and diethanolamine with four ß-hydroxyalkylamide groups per molecule
- trans content at the cyclohexyl ring of greater than or equal to 70 mol%, preferably greater than 80 mol% and particularly preferably greater than 85 mol%.
- Powder coating composition is the ratio of ß-hydroxyalkylamide groups to the carboxylate groups of the polymers containing carboxylate groups preferably from 0.5 to 1.5: 1, more preferably from 0.8 to 1.2: 1.
- the powder coating composition the customary in powder coating technology auxiliaries and additives C), such as leveling agents, for.
- leveling agents for.
- polysilicone or acrylates light stabilizers z. Sterically hindered amines and / or absorbers,
- Degassing agents for example benzophenone
- modified phenolic resins for example benzophenone
- catalysts and / or other auxiliaries such as.
- Fillers and pigments such. Titanium dioxide may be added in an amount of up to 50% by weight of the total composition.
- the powder coating compositions are quantitatively composed as follows:
- the powder coating compositions according to the invention have good storage stability at temperatures of 30 ⁇ 1 or 40 ⁇ 1 ° C. in the storage test according to DIN EN ISO 8130-8 customary for powder coatings, and are storable for> 30 days.
- the powder coating compositions according to the invention contain:
- At least one carboxylate-containing polyester having an acid number of 15 to 150 mg / KOH / g and a glass transition temperature of at least 40 ° C,
- At least one ⁇ -hydroxyalkylamide according to the invention having at least two or more, preferably four ⁇ -hydroxyalkylamide groups, or else mixtures thereof having the same and / or different functionality,
- Adjuvants e.g. Wetting, leveling or degassing agents, heat or UV stabilizers, pigments, dyes, fillers, co-crosslinkers.
- the invention relates to a process for the preparation of a
- Powder coating composition substantially containing
- At least one carboxylate group-containing polymer having an acid number of 5 to 250 mg KOH / g, and a glass transition temperature T g of greater than 40 ° C, and
- R 3 independently of one another identical or different radicals selected from hydrogen, alkyl radical, cycloalkyl radical, aryl radical, aralkyl radical or alkenyl radical having 1 to 24 carbon atoms, which radicals may also contain heteroatoms and / or functional groups, and where two or more radicals selected from hydrogen, alkyl radical, cycloalkyl radical, aryl radical, aralkyl radical or alkenyl radical having 1 to 24 carbon atoms, which radicals may also contain heteroatoms and / or functional groups, and where two or more
- Substituents R 3 may be linked together to form rings
- ⁇ -hydroxyalkylamides are below 150 ° C in solid form
- Powder coating composition wherein as component B) N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1, 4-diamide according to the formula XI IA is contained,
- DSC differential scanning calorimetry
- the invention also provides a process for the preparation of a
- DSC differential scanning calorimetry
- endothermic peak 2 is 1: 1 to 1: 5
- the preparation of the powder coating composition of the invention is preferably carried out in the melt by coextrusion of all
- Powder coating compositions thus consist of the matrix obtained by coextrusion of all the components.
- Example (8) with the polyacrylate differs therefrom, since more crosslinker is needed for the increased acid number and a lower pigmentation was chosen due to the expected higher brittleness.
- Coatings are carried out by conventional methods for powder coatings, preferably by means of an electrostatic powder coating spray device by the triboelectric or corona process or by the fluidized bed process.
- the powder coating compositions according to the invention have a good storage stability and show after crosslinking between 150 to 220 ° C good paint properties, optically good surfaces and the described low gloss levels.
- Polyacrylate mixture (one-shot blend) are needed.
- At least one carboxylate group-containing polymer having an acid number of 5 to 350 mg KOH / g, and a glass transition temperature T g of greater than 40 ° C,
- radicals independently of one another are identical or different radicals selected from the group consisting of alkyl radical, cycloalkyl radical, aryl radical, aralkyl radical or alkenyl radical having 1 to 24 carbon atoms, where the radicals can also contain heteroatoms and / or functional groups, and where R 1 can also be hydrogen, and where R 2 also be identical or different radicals selected from the group consisting of alkyl radical, cycloalkyl radical, aryl radical, aralkyl radical or alkenyl radical having 1 to 24 carbon atoms, where the radicals can also contain heteroatoms and / or functional groups, and where R 1 can also be hydrogen, and where R 2 also
- R 3 independently of one another identical or different radicals selected from hydrogen, alkyl radical, cycloalkyl radical, aryl radical, aralkyl radical or alkenyl radical having 1 to 24 carbon atoms, which radicals may also contain heteroatoms and / or functional groups, and where two or more radicals selected from hydrogen, alkyl radical, cycloalkyl radical, aryl radical, aralkyl radical or alkenyl radical having 1 to 24 carbon atoms, which radicals may also contain heteroatoms and / or functional groups, and where two or more
- Substituents R 3 may be linked together to form rings
- ⁇ -hydroxyalkylamides are below 150 ° C in solid form; C) optional adjuvants and / or additives; wherein the ratio of ⁇ -hydroxyalkylamide groups to the carboxylate groups is between 0.5: 1 to 1.5: 1;
- Very particularly preferred subject of the invention is a
- a powder coating composition comprising the compound N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1,4-diamide according to the formula XIIA as component B),
- a trans content of the cyclohexyl ring of greater than or equal to 70 mol%, based on the total amount of all present isomers of N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1,4-diamide,
- peak 1 is in the range of 140-170 ° C with a maximum of 155-165 ° C
- peak 2 in the range of 170-210 ° C has a maximum of 175-207 ° C
- Particularly preferred subject of the invention is a
- Powder coating composition wherein as component B) the ⁇ -hydroxyalkylamide N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1, 4-diamide according to the formula XIIA is included, having a trans content of the cyclohexyl ring of greater than or equal to 70 mol%, preferably greater than 80 mol% and particularly preferably greater than 85 mol%, based on the total amount of all the isomers of ⁇ , ⁇ , ⁇ ', ⁇ '-tetrakis (2-hydroxyethyl) cyclohexyl 1, 4-diamids.
- this ⁇ -hydroxyalkylamide according to the invention used as component B), has N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1,4-diamide according to the formula XI IA, two endothermic peaks according to DSC analysis, ( differential scanning calorimetry): first a peak with a maximum (peak 1) of about 160 ° C and another second peak with a maximum (peak 2) at about 190 ° C, they are the illustrations for the examples.
- the first peak is in the range of 140-170 ° C with a maximum of 155-165 ° C and the second peak is in the range of 170-210 ° C with a maximum of 175-207 ° C. More preferably, the first peak is in the range of 155-170 ° C with a maximum of 158-165 ° C and the second peak is in the range of 170-210 ° C with a maximum of 180-205 ° C.
- the ratio of enthalphies from endothermic peak 1 (-160 ° C.) to endothermic peak 2 (-190 ° C.) can be 1: 1 to 1: 5, preferably 1: 1 to 1: 3.
- the DSC measurements were carried out in accordance with DIN EN ISO 1 1357-1 of March 2010.
- a heat flow differential calorimeter manufactured by Mettler-Toledo model DSC 821 was used. The samples are run once from -30 ° C to 250 ° C at 10K / min.
- the ⁇ -hydroxyalkylamide of the formula XIIA used as component B) according to the invention is below 175 ° C., preferably below 180 ° C. and more preferably below 185 ° C., in solid form.
- the ⁇ -hydroxyalkylamide of the formula XIIA according to the invention used as component B) with the features 1. to 4. was investigated by an X-ray structure analysis of a single crystal. Detailed information on the measurement is available in the
- the values in the bracket indicate the measurement accuracy in plus and minus for the corresponding last digit and last two digits, respectively.
- Very particularly preferred subject of the invention is a
- Powder coating composition containing the compound ⁇ , ⁇ , ⁇ ', ⁇ '-tetrakis (2) hydroxyethyl) cyclohexyl-1,4-diamide according to the formula XIIA as component B),
- a trans content of the cyclohexyl ring of greater than or equal to 70 mol%, based on the total amount of all present isomers of N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1,4-diamide,
- peak 1 is in the range of 140-170 ° C with a maximum of 155-165 ° C
- peak 2 in the range of 170-210 ° C has a maximum of 175-207 ° C
- N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1,4-diamide used as component B) according to the formula XIIA can be obtained by various processes:
- the N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1,4-diamide according to the formula XIIA in an extruder, intensive kneader, intensive mixer or static Mixer, preferably in an extruder, preferably solvent-free, prepared. Temperatures of 100 to 180 ° C are used. This is followed by recrystallization in a suitable solvent, preferably water. After dissolving at
- This can then be subsequently washed with alcohols, preferably methanol and dried.
- alcohols preferably methanol and dried.
- the drying takes place at temperatures of 20-90 ° C, and can also be carried out at a vacuum.
- a further variant of the preparation is carried out as described in more detail above, characterized in that the N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1,4-diamide according to the formula XIIA in an extruder, intensive Kneader, intensive mixer or static mixer, preferably in an extruder, preferably solvent-free, is produced. Temperatures of 100 to 180 ° C are used. Subsequently, a heat treatment at temperatures of 50 - 100 ° C, preferably at temperatures of 70 - 85 ° C. The period is more than 6 hours, preferably more than 12 hours. The heat treatment can be carried out in vacuo.
- N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1, 4-diamide used as component B) according to the formula XIIA can also be used as component B) according to the formula XIIA.
- the reaction is carried out in conventional reactors. It can be used without pressure, using a reflux condenser, or under pressure with the reactor closed.
- the synthesis is carried out in a solvent, preferably in alcohols, preferably methanol.
- the added amount of solvent is greater than 10 wt .-%, preferably greater than 15 wt .-%, based on the total amount of all starting materials used (starting materials). In this case, under reflux, or even at lower temperatures, and higher temperatures, under pressure, can be used.
- the preparation is carried out at temperatures of 20 to 120 ° C, preferably at 60 to 90 ° C, particularly preferably at 70 to 85 ° C.
- N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1, 4-diamide according to the formula XIIA can be in suitable Solvents, preferably in water or alcohols, preferably in methanol, are recrystallized.
- N, N, N ', N'-tetrakis- (2-hydroxyethyl) cyclohexyl-1, 4-diamide according to the formula XIIA can also be carried out batchwise without solvent.
- the reaction is carried out in conventional reactors. It can under
- the preparation is carried out at temperatures of 20 to 140 ° C, preferably 60 to 90 ° C, more preferably at 70 to 85 ° C.
- suitable solvents preferably in water or alcohols, preferably in methanol. You get after the
- the concentration of all isomers of N, N, N ', N'-tetrakis- (2-hydroxyethyl) cyclohexyl-1, 4-diamide in the final product after its preparation is 75% by mass, preferably 80% by mass and more preferably 85% by mass -%.
- the invention is also the use of a
- DSC differential scanning calorimetry
- endothermic peak 2 is 1: 1 to 1: 5
- the invention is also the use of a
- Powder coating composition as described above, wherein as component B) ⁇ , ⁇ , ⁇ ', ⁇ '-tetrakis (2-hydroxyethyl) cyclohexyl-1, 4-diamide according to the formula XIIA is included,
- a trans content of the cyclohexyl ring of greater than or equal to 70 mol%, based on the total amount of all present isomers of N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1,4-diamide,
- peak 1 is in the range of 140-170 ° C with a maximum of 155-165 ° C
- peak 2 in the range of 170-210 ° C has a maximum of 175-207 ° C
- Titanium dioxide Kronos® 2160 (Kronos Titan GmbH, D)
- Resiflow® PV 88 (Worlee-Chemie GmbH, D)
- the gloss can be maintained in low admixtures or, if desired, be shifted to higher values with increased addition or exchange. Shown here in Examples 9 to 13 using a polyester.
- Terephthalic acid diglycidyl ester and trimellitic triglycidyl ester (trade names, eg, ARALDIT PT 910 and PT 912, Huntsman), glycidyl ester of versatic acid (Trade name eg CARDURA E10, Shell), 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate (ECC), diglycidyl ether based on bisphenol A
- Such co-crosslinkers can be up to 50 wt .-% of the used
- the DSC measurements were carried out in accordance with DIN EN ISO 1 1357-1 of March 2010.
- Calibrant substances including source, mass and other properties of importance for calibration
- Example 3b The product prepared in 3a is dissolved in boiling water, then slowly cooled again and after crystallization briefly washed with methanol. Table 3a This product shows the two endothermic peaks, see Figure 2, with existing matting effect in the resulting powder coatings of 29 divisions at 60 degrees, Table 3a.
- stream 1 consisted of DMCD
- Stream 3 consisted of the catalyst, the methanolic sodium methylate solution.
- the material flows were metered so that the molar ratio between dimethyl-1, 4-cyclohexyldicarboxylate and diethanolamine 1: 1, 95.
- the total amount of catalyst (only sodium methylate, calculated solvent-free) based on the total formulation was 0.50 to 3.0%.
- Stream 1 was added to the first housing at a rate of 10.0 kg / hr
- Twin-screw extruder (ZSK 30, 32 d) fed (temperature of the stream 80 to 130 ° C).
- Stream 3 was injected from inlet to the extruder into Stream 2 (0.5 to 2.0 kg / hr).
- the extruder used consisted of 8 housings which could be heated and cooled separately. Housing 1 - 5: 160 ° C, housing 6 - 8: 120 - 160 ° C.
- the housings 3, 5 and 8 were provided with a vacuum dome (100 to 600 mbar).
- the extruder screws were equipped with conveying elements.
- Vacuum domes were kneading blocks installed.
- the end product was cooled down a pipe section or via an extruder and passed to a cooling belt and cooled further.
- Example 4a recrystallized.
- the product from Example 4a is dissolved in demineralized water under boiling and then slowly cooled and crystallized, so as to be converted back into the solid form.
- the following is washed with methanol and dried at about 20 mbar and 50 ° C in a vacuum oven.
- Table 4 Thus, an N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1,4-diamide having two endothermic peaks (1st at about 160 ° C and 2nd at about 190 ° C) is obtained DSC.
- N, N, N ', N'-tetrakis (2-hydroxyethyl) cyclohexyl-1,4-diamide not according to the invention was prepared by the DSC according to FIG. 4.
- This product thus prepared is run on a cooling belt and collected. This material is then annealed in a drying oven at 80 ° C for 24 h under vacuum and then comminuted the product thus obtained.
- a ⁇ -hydroxyalkylamide of the formula XIIA was prepared as in Example 3a. From this, a single crystal was grown.
- the formula XIIA according to the invention was investigated by an X-ray structure analysis of a single crystal. Detailed information on the measurement is summarized in Appendix 1.
- the data collection was performed in phi and omega scans. Data collection and reduction were done with Crysalis (Oxford Diffraction 2007).
- Table a Crystal data and structural refinement data for vesta.
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
Description
Claims
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
RU2012143306/05A RU2012143306A (ru) | 2010-03-11 | 2011-03-10 | Отверждаемые при нагревании композиции порошкового лака, которые после отверждения покрытия приводят к матовой поверхности, а также простой способ их получения |
EP11707677A EP2545115A1 (de) | 2010-03-11 | 2011-03-10 | Bei hitze härtende pulverlackzusammensetzungen, welche nach aushärtung der beschichtung zu einer matten oberfläche führen, sowie ein einfaches verfahren zu ihrer herstellung |
JP2012556525A JP5730336B2 (ja) | 2010-03-11 | 2011-03-10 | コーティングの硬化後に艶消し表面となる熱硬化性の粉末塗料組成物並びにその簡単な製造方法 |
US13/583,252 US20130041103A1 (en) | 2010-03-11 | 2011-03-10 | Heat-curable powder coating compositions, which after the coating has cured result in a matt surface and simple method for producing same |
AU2011226101A AU2011226101B2 (en) | 2010-03-11 | 2011-03-10 | Heat-curable powder coating compositions, which after the coating has cured result in a matt surface and simple method for producing same |
CA2791295A CA2791295A1 (en) | 2010-03-11 | 2011-03-10 | Heat-curable powder coating compositions, which after the coating has cured result in a matt surface and simple method for producing same |
KR1020127023598A KR20130039715A (ko) | 2010-03-11 | 2011-03-10 | 코팅이 경화된 후에 무광택 표면을 생성하는 열경화성 분말 코팅 조성물 및 그의 간단한 제조 방법 |
CN201180013491.8A CN102782032B (zh) | 2010-03-11 | 2011-03-10 | 在涂料固化后产生消光表面的在加热时固化的粉末涂料组合物及其简单制造方法 |
BR112012022874-9A BR112012022874A2 (pt) | 2010-03-11 | 2011-03-10 | composições de lacas em pós curáveis por calor, seu processo de produção e uso das mesma |
MX2012010450A MX2012010450A (es) | 2010-03-11 | 2011-03-10 | Composiciones de revestimiento en polvo termocurables, que despues de curado del revestimiento, resultan en una superficie mate y un metodo simple para producir las mismas. |
HK13105684.5A HK1177945A1 (en) | 2010-03-11 | 2013-05-13 | Heat-curable powder coating compositions, which after the coating has cured result in a matt surface and simple method for producing same |
Applications Claiming Priority (2)
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DE102010002785.5 | 2010-03-11 | ||
DE102010002785 | 2010-03-11 |
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WO2011110640A1 true WO2011110640A1 (de) | 2011-09-15 |
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PCT/EP2011/053639 WO2011110640A1 (de) | 2010-03-11 | 2011-03-10 | Bei hitze härtende pulverlackzusammensetzungen, welche nach aushärtung der beschichtung zu einer matten oberfläche führen, sowie ein einfaches verfahren zur ihrer herstellung |
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US (4) | US8476376B2 (de) |
EP (1) | EP2545115A1 (de) |
JP (1) | JP5730336B2 (de) |
KR (1) | KR20130039715A (de) |
CN (1) | CN102782032B (de) |
AU (1) | AU2011226101B2 (de) |
BR (1) | BR112012022874A2 (de) |
DE (1) | DE102011005369A1 (de) |
HK (1) | HK1177945A1 (de) |
MX (1) | MX2012010450A (de) |
RU (1) | RU2012143306A (de) |
WO (1) | WO2011110640A1 (de) |
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US8476376B2 (en) * | 2010-03-11 | 2013-07-02 | Evonik Degussa Gmbh | Heat-curing powder-lacquer compositions yielding a matte surface after curing of the coating, as well as a simple method for production of same |
US20110224459A1 (en) | 2010-03-11 | 2011-09-15 | Evonik Degussa Gmbh | Beta-hydroxyalkylamides, a method for production of same and use of same |
EP2426160B1 (de) * | 2010-09-03 | 2014-01-15 | Sika Technology AG | Hitzehärtende Epoxidharzzusammensetzung mit Wasser als Treibmittel |
DE102010041247A1 (de) | 2010-09-23 | 2012-03-29 | Evonik Degussa Gmbh | Verfahren zur Herstellung von lagerstabilen Polyurethan-Prepregs und daraus hergestellte Formkörper aus Polyurethanzusammensetzung in Lösung |
DE102011006163A1 (de) | 2011-03-25 | 2012-09-27 | Evonik Degussa Gmbh | Lagerstabile Polyurethan-Prepregs und daraus hergestellte Formkörper aus Polyurethanzusammensetzung mit flüssigen Harzkomponenten |
DE102012219324A1 (de) | 2012-10-23 | 2014-04-24 | Evonik Industries Ag | Zusammensetzungen umfassend alkoxysilanhaltige Isocyanateund saure Stabilisatoren |
CN103756259B (zh) * | 2014-01-03 | 2016-05-25 | 交通运输部公路科学研究所 | 一种沥青混合料干法改性剂、其制备方法及沥青混合料 |
WO2016012252A1 (en) * | 2014-07-25 | 2016-01-28 | Dsm Ip Assets B.V. | Matt powder coatings |
JP2016084466A (ja) * | 2014-10-27 | 2016-05-19 | 関西ペイント株式会社 | 粉体塗料組成物及び塗膜形成方法 |
JP2016176053A (ja) * | 2015-03-18 | 2016-10-06 | 関西ペイント株式会社 | 粉体塗料組成物及び塗膜形成方法 |
EP3255039B1 (de) | 2016-06-10 | 2018-12-12 | Evonik Degussa GmbH | Verfahren zur herstellung von 2-(2,2,6,6-tetramethylpiperidin-4-yl)propan-1,3-diamin |
ES2696529T3 (es) | 2016-06-10 | 2019-01-16 | Evonik Degussa Gmbh | Composición de resina epoxi que contiene 2-(3-(aminometil)-3,5,5-trimetilciclohexil)propan-1,3-diamina (AM-CPDA) como endurecedor |
ES2702751T3 (es) | 2016-06-10 | 2019-03-05 | Evonik Degussa Gmbh | 2-(3-(aminometil)-3,5,5-trimetilciclohexil)propan-1,3-diamina, un procedimiento de preparación y uso |
EP3263616B8 (de) | 2016-06-27 | 2020-01-15 | Evonik Operations GmbH | Alkoxysilan-funktionalisierte allophanat-haltige beschichtungsmittel |
MX2019004555A (es) | 2016-10-19 | 2019-08-05 | Swimc Llc | Aditivos de resinas solubles en alcali y composiciones del revestimiento que incluyen tales aditivos. |
CN114621617A (zh) * | 2020-12-08 | 2022-06-14 | 梧州市泽和高分子材料有限公司 | 一种用于β-羟烷基酰胺粉末涂料的消光助剂 |
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- 2011-03-10 US US13/583,252 patent/US20130041103A1/en not_active Abandoned
- 2011-03-10 CN CN201180013491.8A patent/CN102782032B/zh not_active Expired - Fee Related
- 2011-03-10 WO PCT/EP2011/053639 patent/WO2011110640A1/de active Application Filing
- 2011-03-10 AU AU2011226101A patent/AU2011226101B2/en not_active Ceased
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2013
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Also Published As
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US20140316056A1 (en) | 2014-10-23 |
CN102782032B (zh) | 2014-12-24 |
US20110288202A1 (en) | 2011-11-24 |
KR20130039715A (ko) | 2013-04-22 |
US9096774B2 (en) | 2015-08-04 |
EP2545115A1 (de) | 2013-01-16 |
US20130041103A1 (en) | 2013-02-14 |
US8476376B2 (en) | 2013-07-02 |
JP2013522383A (ja) | 2013-06-13 |
US20110224378A1 (en) | 2011-09-15 |
BR112012022874A2 (pt) | 2018-06-05 |
JP5730336B2 (ja) | 2015-06-10 |
DE102011005369A1 (de) | 2011-09-15 |
CN102782032A (zh) | 2012-11-14 |
AU2011226101A1 (en) | 2012-08-23 |
MX2012010450A (es) | 2012-12-05 |
RU2012143306A (ru) | 2014-04-20 |
US8524837B2 (en) | 2013-09-03 |
AU2011226101B2 (en) | 2014-03-06 |
HK1177945A1 (en) | 2013-08-30 |
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