WO2009013064A2 - Compositions de matière de revêtement - Google Patents

Compositions de matière de revêtement Download PDF

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Publication number
WO2009013064A2
WO2009013064A2 PCT/EP2008/057370 EP2008057370W WO2009013064A2 WO 2009013064 A2 WO2009013064 A2 WO 2009013064A2 EP 2008057370 W EP2008057370 W EP 2008057370W WO 2009013064 A2 WO2009013064 A2 WO 2009013064A2
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Prior art keywords
acid
mol
coating material
material compositions
weight
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PCT/EP2008/057370
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German (de)
English (en)
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WO2009013064A3 (fr
Inventor
Patrick GLÖCKNER
Andreas Wenning
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Evonik Degussa Gmbh
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Publication of WO2009013064A2 publication Critical patent/WO2009013064A2/fr
Publication of WO2009013064A3 publication Critical patent/WO2009013064A3/fr

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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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C09D11/104—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • 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
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • 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
    • C09D5/004—Reflecting paints; Signal paints
    • 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
    • C09D5/08—Anti-corrosive paints
    • 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
    • C09D5/34—Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
    • C09K2200/0655—Polyesters

Definitions

  • the invention relates to coating compositions z.
  • Unsaturated polyester resins are known. They are prepared by condensation of saturated and unsaturated dicarboxylic acids or their anhydrides with diols. Their properties depend largely on the type and amount ratio of the starting materials.
  • the carriers of the polymerizable double bonds are generally ⁇ , ⁇ -unsaturated acids, primarily maleic acid or its anhydride or fumaric acid; Unsaturated diols are of minor importance.
  • the reactive double bonds in the polyester molecule are therefore "diluted" by condensing in them saturated aliphatic or aromatic dicarboxylic acids.
  • Alcohol components used are straight-chain and / or branched diols
  • the individual UP resin types differ not only in the components used for their preparation but also in the quantitative ratio from saturated to unsaturated acids, which determines the crosslink density in the polymerization, the degree of condensation, ie the molecular weight, the acid and OH number, ie the nature of the end groups in the chain molecules, the
  • Coating composition compositions containing unsaturated polyesters as adhesion-promoting component are known from DE 24 09 800, EP 114 208 and EP 934 988 and DE 102 42 265.
  • Benzene is listed in accordance with the Technical Rules for Hazardous Substances (TRGS 905, list of carcinogenic, mutagenic or reprotoxic substances) with K1 and M2. Accordingly, it is desirable to dispense with benzene-containing products.
  • Formaldehyde can cause health problems. However, an exact classification is not yet made.
  • IARC International Agency for Research on Cancer
  • WHO World Health Organization
  • VOC volatile organic compounds
  • Coating substance compositions which are suitable for metallic, mineral substrates or for substrates made of wood, paper and plastics.
  • the coating compositions should also have a very good adhesion, even under critical climatic conditions high corrosion protection, high gloss, high solids content or a low viscosity at a given solids content and a very good stone chip resistance and resistance to salt solutions and be largely free of benzene and formaldehyde ,
  • the invention relates to coating compositions essentially containing
  • the content of benzene is less than 10 mg / kg and the content of formaldehyde is less than 10 mg / kg, relative to the polyester,
  • the polydispersity of the molecular weight distribution of the polyester is between 1, 3 and 4.5, and
  • the tricyclodecane (mono- / di-) aldehyde content in the dicidol mixture C) is less than 2% by weight
  • the content of mono (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane in the dicidol mixture C) is less than 10% by weight
  • the content of the metals chromium, nickel, copper, cadmium, lead and rhodium in the mixture of diclides C) is in each case less than 2 mg / kg, and
  • the coating material compositions thus obtained are characterized in that they • have very good adhesion to metallic, mineral substrates and / or to substrates made of wood, paper and / or plastics, even under critical climatic conditions,
  • a very good adhesion to metallic, mineral substrates and / or substrates made of wood and / or plastics even under critical climatic conditions, a high corrosion protection effect, a high resistance to salt solutions and a very good stone chip resistance is surprisingly achieved significantly by adjusting the following parameters:
  • the surface tension of the coating material composition must always be lower than that of the substrate to be coated, so that the substrate can be optimally wetted by the coating material.
  • the surface tension of the coating composition according to the invention can be adjusted by the addition of the inventive yellowing-resistant, low-viscosity, unsaturated, amorphous polyester 1, which are largely free of benzene and formaldehyde.
  • urethane groups OH groups (metals, plastic substrates) or salt-forming groups (eg., Carbonklare weakness) (metal substrates) in the molecular structure.
  • the lowest possible glass transition temperature of the film formers, which during processing and crosslinking is below the processing / regeneration temperature, supports the orientation of the functional groups to the substrate.
  • the adsorption between film and substrate can be improved by the addition of the invention essential, yellowing resistant, low-viscosity, unsaturated, amorphous polyesters, which are largely free of benzene and formaldehyde.
  • the polyesters essential to the invention have an acid number between 1 and 200 mg KOH / g, preferably between 1 and 100, more preferably between 1 and 50 mg KOH / g and an OH number between 1 and 500 mg KOH / g, preferably between 1 and 200, more preferably between 1 and 100 mg KOH / g.
  • the Tg of the unsaturated amorphous polyester 1 varies from -30 to +90 0 C, preferably from -20 to +80 0 C, more preferably - 10 to + 75 0 C.
  • Coating composition in absorbent substrates such. As wood or paper penetration of the coating material in the ground. Since there is thus a “gearing" between the coating material and the substrate, the adsorption and thus the adhesion is further improved.
  • volume shrinkage / internal stress Particularly in the case of solvent-borne coating compositions (hot-seal coatings, hot melt adhesives, radiation-curable coating compositions), the volume shrinkage that occurs during crosslinking reduces adhesion to a particular degree. It can be explained by the fact that the distance of the film former in the uncured state is greater than after the chemical cross-linking, in which covalent single bonds are formed. The volume shrinkage is the more pronounced, the higher the functionality and the lower the molecular weight and the standing claim of the film former. Since low molecular weight film formers have a very high functionality in relation to their molecular weight, their influence on the volume shrinkage is correspondingly high.
  • the temperature during curing varies between room temperature (about 20 ° C) and 250 ° C.
  • the glass transition temperature (Tg) of the forming film is below the cure temperature, the film may change shape, i. H. relax, whereby the influence of the volume shrinkage on the adhesion is rather low.
  • Tg glass transition temperature
  • the Tg of the film forming rises above the curing temperature, internal tensions arise due to the crosslinking and the volume shrinkage associated therewith, which can lead to delamination of the coating from the substrate (delamination). Accordingly, it must be ensured that the coating can reduce these internal stresses (relax), what z. B. by adjusting the Tg of the binder 2nd and the film succeeds.
  • the mechanical properties eg hardness-elasticity balance
  • the glass transition temperature of the forming Films optimally adjusted to the selected curing temperature and reduces the volume shrinkage.
  • polyesters 1 according to the invention can be homogeneously mixed in solution or melt with binders 2.
  • binders 2 Polyacrylates, saturated and / or unsaturated polyesters and copolyesters, derivatives of cellulose such.
  • alkali metal silicates eg., Water glass
  • polyvinyl chloride and its derivatives such as copolymers and terpolymers, chlorinated rubbers, chlorinated polyesters, PVDF and give after application and evaporation of any solvents present clear and transparent films.
  • polyesters 1 to improve the adhesion of coating compositions, predestines them for corrosion protection. In addition to increasing adhesion to the substrate, intercoat adhesion to overlying boundary layers is also improved. Another advantage of the polyester is the high resistance to hydrolysis. Coating compositions which contain a polyester 1 according to the invention also have a high gloss and a good flow. In spray paints, the spray mist absorption is also significantly increased.
  • the constituent polyester 1 according to the invention can be present in amounts of from 0.1 to 80, preferably from 1 to 50, particularly preferably from 1 to 20,% by weight in the coating material compositions according to the invention.
  • the inventively essential yellowing resistant, low-viscosity, unsaturated, amorphous polyesters which are largely free of benzene and formaldehyde, are obtained by reacting the alcohol component and the acid component.
  • the essential to the invention yellowing, low viscosity, unsaturated, amorphous polyesters, which are largely free of benzene and formaldehyde, contain as acid component I. At least one ⁇ , ß-unsaturated dicarboxylic acid A).
  • the unsaturated polyester resins contain citraconic, fumaric, itaconic, maleic and / or mesaconic acid or their derivatives such as.
  • anhydrides and / or low molecular weight alkyl esters such. For example, methyl and / or ethyl esters. It can also be used mixtures.
  • the acid component I may contain further linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic di- and / or polyfunctional carboxylic acids B) which have no ⁇ , ⁇ -unsaturated Have groupings. Suitable are all di- and / or higher functional carboxylic acids such.
  • Phthalic acid isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, sebacic acid, Methyltetra-, methylhexahydrophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dodecanedioic acid, adipic acid, azelaic acid, pyromellitic acid and / or trimellitic acid and derivatives thereof such.
  • anhydrides and / or low molecular weight alkyl esters such. For example, methyl and / or ethyl esters.
  • phthalic acid trimellitic acid
  • methylhexahydrophthalic acid hexahydrophthalic acid
  • tetrahydrophthalic acid adipic acid and / or azelaic acid and derivatives thereof
  • anhydrides and / or low molecular weight alkyl esters such as methyl and / or ethyl esters.
  • Particularly preferred are phthalic acid, trimellitic acid, methylhexahydrophthalic acid, hexahydrophthalic acid and / or adipic acid and derivatives thereof such.
  • anhydrides and / or low molecular weight alkyl esters such.
  • methyl and / or ethyl esters It can also be used mixtures.
  • Monocarboxylic acids as acid component I. B), such as. B. isononanoic acid, 2-ethylhexanoic acid, benzoic acid, derivatives of benzoic acid such as. B. tert-butyl benzoic acid are contained in a subordinate framework in amounts below 10 mol%, based on the acid component I., since they represent chain terminators, which reduce the OH or COOH functionality.
  • the acid component can consist partly or completely of anhydrides and / or alkyl esters, preferably methyl esters.
  • a Dicidolgemisch C As alcohol component II. Essentially essential to the invention a Dicidolgemisch C) is used. Preferred is a Dicidolgemisch C) of the isomeric compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane and 5,8-bis (hydroxymethyl ) Tricyclo [5.2.1.0 26 ] decane, wherein each isomer may be present in a proportion of 20 to 40 wt .-% in the mixture and the sum of the three isomers 90 to 100 wt .-%, preferably 95 to 100 wt %, and the mixture is at least 5 mol% in the alcohol component II of the polyester.
  • the isomer content of the Dicidolgemisches C) can qualitatively and quantitatively z. B. by GC analysis or quantitatively by separation by preparative GC or HPLC and subsequent NMR spectroscopy can be determined. All corresponding isomers of dicidol in the 9-position are just as suitable, but due to the mirror symmetry of the above isomers, as well as the cis and trans isomers, indistinguishable under normal, practical circumstances.
  • Dicidolgemisch C may contain up to 10% further isomers of diclidol and / or trimeric and / or higher isomeric diols of the Diels-Alder reaction product of cyclopentadiene.
  • the alcohol component II From 20 mol%, from 50 mol%, preferably from 90 mol%, more preferably from 100 mol% Dicidolgemisch C), this particularly preferably 95 to 100 wt .-% of the isomeric compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane and 5,8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane contains.
  • Dicidol is produced from the Diels-Alder product of cyclopentadiene, dicyclopentadiene, which is converted into the dialdehyde in an oxo synthesis using CO / H 2 at elevated temperature and pressure.
  • the catalysts used are transition metal compounds of the metals of group VIII of the Periodic Table of the Elements (cf .. EP 1 529 768, DE 103 57 718). Subsequently, the dialdehyde is converted by hydrogenation in the diol.
  • the dicidol mixture C) essential to the invention has a small proportion of metals contained in the preparation.
  • a check of the metal content can z. B. by atomic absorption spectroscopy (AAS).
  • AAS atomic absorption spectroscopy
  • Dicidolgemisch C which contains less than 2, preferably less than 1 wt .-% tricyclodecane (mono- / di-) aldehyde.
  • the content can be determined qualitatively and / or quantitatively by gas chromatographic analysis (GC) optionally in combination with mass spectrometry (MS).
  • GC gas chromatographic analysis
  • MS mass spectrometry
  • the dicidol mixture C) may also contain monoalcohols (cf., DE 103 57 718 p. 4 [0014]). Since these represent chain terminators and thus reduce the content of functional end groups, which adhesion properties can be adversely affected (poor interaction with the substrate (eg, enter acid groups interactions with metal substrates)) and optionally desired crosslinking reactions with z.
  • the content of the mono (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane is below 10, preferably below 5, especially below 3 mol% based on the alcohol component Dicidolgemisch C).
  • the content can be determined qualitatively and / or quantitatively by gas chromatographic analysis (GC) optionally in combination with mass spectrometry (MS).
  • the content of benzene in the dicidol mixture C) essential to the invention and thus in the polyester essential to the invention is below 10 mg / kg, preferably below 5 mg / kg, more preferably below 3 mg / kg and the content of formaldehyde below 10 mg / kg, preferably less than 5 mg / kg, more preferably less than 2 mg / kg. That this is not trivial, is shown in Example 1 of DE-AS-1 618 384, according to which dicyclopentadiene is hydroformylated as a 25 wt .-% benzene solution.
  • the alcohol component II In addition to the Dicidolgemisch C), the alcohol component II.
  • Preferred additional alcohols D) are ethylene glycol, 1, 2 and / or 1, 3-propanediol, diethylene, dipropylene, triethylene, tetraethylene glycol, 1, 2 and / or 1, 4-butanediol, 1, 3
  • Monoalcohols such. B. hexanol are contained in the subordinate frame in amounts below 10 mol% based on the alcohol component, since they represent chain terminators that reduce the OH or COOH functionality.
  • the alcohol component II In a molar ratio of 0.5 to 2.0 to 1 to the acid component I., preferably 0.8 to 1, 5 to 1. Particularly preferably the reaction of the alcohol component in the molar ratio of 1, 0 to 1, 1 to 1 to the acid component instead.
  • the inventive yellowing-resistant, low-viscosity, unsaturated, amorphous polyesters 1, which are largely free of benzene and formaldehyde, consist of an alcohol component having at least 90 mol%, preferably 95 mol%, particularly preferably 100 mol%. % of the described Dicidolgemisches C) and from fumaric acid and / or maleic acid (anhydride).
  • the polyesters 1 contain the o. G.
  • a further acid B selected from adipic acid or phthalic acid (anhydhd), wherein the ratio of the ⁇ , ß-unsaturated acid A) to the additional acid B) of 2 to 1 to 1 to 4 can vary , Ratios of about 1 to 1 to 1 to 3 are preferred.
  • the polyesters 1 generally have acid numbers of 1 to 200 mg KOH / g, preferably 1 - 100 mg KOH / g, more preferably 1-50 mg KOH / g, OH numbers from 1 to 500 mg KOH / g, preferably 1 - 200 mg KOH / g, more preferably 1-100 mg KOH / g and a Glass transition temperature (Tg) of -30 to +90 ° C, preferably -20 to +80 0 C, more preferably -10 to +75 0 C on.
  • Tg Glass transition temperature
  • Polymers usually do not have an exact molecular weight but a molecular weight distribution (dimer, trimer, tetramer, etc.).
  • the breadth of the distribution is described by the polydispersity, which is the ratio of weight average (Mw) to number average molecular weight (Mn) [Odian, George, P ⁇ nciples of Polyme ⁇ zation, Third Edition, John Wiley & Sons, New York, 1991, page 86 ,].
  • Mw weight average
  • Mn number average molecular weight
  • the number average molecular weight (Mn) of the polyesters 1 according to the invention is between 500 and 6,000, preferably 700 and 5,000 g / mol and the weight-average molecular weight (Mw) between 900 and 27,000, preferably 1,000 and 15,000 g / mol.
  • the polydispersity of the molecular weight distribution of the invention significantly en polyester is between 1, 3 and 4.5, preferably between 1, 6 and 4.0, so that the polyester has a low solution viscosity measured at 23 0 C in accordance with DIN EN ISO 3219, as a 60% XyIoI solution between 50 and 5,000 nnPa-s, preferably between 50 and 3,500, more preferably between 100 and 2,500 mPa-s have.
  • the polyesters 1 according to the invention are amorphous and therefore have no crystalline components in the DSC heating curve. In this way, on the one hand, high transparency and clarity, on the other hand a flexible mechanical behavior can be obtained. Also, the compatibility with other components of a coating is positively influenced by the lack of crystallinity.
  • the test is carried out by differential calorimetry (DSC) according to DIN 53 765 from the 2nd heating curve at a heating rate of 10 K / min.
  • the polyesters according to the invention may also contain auxiliaries and additives, preferably selected from inhibitors, water and / or organic solvents, neutralizing agents, surface-active substances, oxygen and / or radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers and initiators, additives for Influence rheological properties such.
  • auxiliaries and additives preferably selected from inhibitors, water and / or organic solvents, neutralizing agents, surface-active substances, oxygen and / or radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers and initiators, additives for Influence rheological properties such.
  • auxiliaries and additives preferably selected from inhibitors, water and / or organic solvents, neutralizing agents, surface-active substances, oxygen and / or radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers and initiators, additives for Influence rheological properties such.
  • the polyesters 1 according to the invention are produced by (semi) continuous or discontinuous esterification and condensation of the acid components I. and the alcohol components II. In a one-stage or multi-stage procedure.
  • the binders 2 are used in amounts of 99.9 to 20, preferably 99 to 50, particularly preferably 99 to 80 wt .-%. Preference is given to binders from the group of polyurethanes, polyacrylates, polyethers, saturated and / or unsaturated polyesters and copolyesters, alkyd resins, polyamides, casein, polyureas, derivatives of cellulose such as. As cellulose nitrate, cellulose ethers and / or Celluloseacetobutyrate, polyvinyl alcohols and derivatives, polyvinyl acetates, polyvinylpyrolidones, (cyclo) rubbers, natural resins, hydrocarbon resins such.
  • aminoplasts e.g., melamine, benzoguanamine resins
  • polyolefins acrylated polyesters, acrylated polyethers, acrylated epoxy resins, urethane acrylates, epoxy resins, resoles, rosin resins, resinates, silicic acid esters and
  • Alkali metal silicates eg waterglass
  • silicone resins e.g. silicone resins and / or chlorine- and / or fluorine-containing polymers, such as, for example, As polyvinyl chloride and its derivatives, chlorinated rubber, chlorinated polyester, PVDF used. It can too Mixtures are used.
  • the binders may be foreign and / or self-crosslinking, air-drying (physically drying) and / or oxidatively curing.
  • the binders may be soluble in organic solvents but also in reactive diluents and / or soluble in water, mixed or dispersible. In principle, all binders which are used in the paint, paints, adhesives and printing inks industry are suitable.
  • the component 3 may optionally be present and is used in amounts of 0 to 80, preferably 0.1 to 70, particularly preferably 0.1 to 60 wt .-%.
  • auxiliaries and additives such as, for example, inhibitors, organic solvents, water, surface-active substances, oxygen and / or radical scavengers, catalysts, light stabilizers, color brighteners,
  • Photosensitizers and initiators additives for influencing rheological properties such.
  • Suitable solvents are those used in the paint, paint, adhesive and
  • Component 4 may optionally be present and is used in amounts of from 0 to 70, preferably from 0.1 to 60, particularly preferably from 1 to 50,% by weight.
  • all colorants and / or fillers which are used in the paint, paints, adhesives and printing inks industry are suitable. They are selected according to coloristic aspects and requirements such.
  • inorganic pigments and fillers such.
  • B. Milohblau titanium dioxide, iron oxides, metal pigments (eg., Spinel, bismuth vanadate, nickel titanium, chromium oxide), carbon blacks and carbonates such.
  • As baryte, blanc fixe calcium sulfates, silicates, such as.
  • talc pyrophyllite, chlorite, mica, kaolin, slate, field column, precipitated Ca, Al, Ca / Al, Na / Al silicates, silicic acids, such as.
  • quartz, quartz, cristobalite, kieselguhr, precipitated and / or fumed silica, glass flour and oxides such.
  • magnesium and aluminum oxides and hydroxides and organic pigments such.
  • isoindoline, azo, Chinachdon-, perylene, dioxazine, phthalocyanine pigments used.
  • metallic effect pigments such.
  • Interference or pearlescent effect pigments such as
  • metal oxide mica pigments, bismuth oxychloride, basic lead carbonate, fish silver or micronized titanium dioxide, platelet-shaped graphite, platelet-shaped iron oxide, multi-layer effect pigments from PVD films or produced by the CVD process (Chemical Vapor Deposition) and diessigkhstall- (polymer) Pigments are used.
  • dyes are used. A list of pigments, fillers and / or dyes used is described in "Römpp Lexikon, Lacke und Druckmaschine, publisher Ulrich Zorll, Georg Thieme Verlag, Stuttgart, 1998 "or” Pigment and Grestofftabellen, published by Olaf Lückert, Vincentz Verlag, Hannover, 2002 ".
  • the invention also provides a process for the preparation of coating compositions comprising substantially 1. 0.1 to 80 wt .-% of a yellowing-resistant, low-viscosity, unsaturated, amorphous polyester, which is largely free of benzene and formaldehyde, consisting of
  • the content of benzene is less than 10 mg / kg and the content of formaldehyde is less than 10 mg / kg, relative to the polyester,
  • the polydispersity of the molecular weight distribution of the polyester is between 1, 3 and 4.5, and
  • the tricyclodecane (mono- / di-) aldehyde content in the dicidol mixture C) is less than 2% by weight
  • the content of mono (hydroxymethyl) thcyclo [5.2.1.0 26 ] decane in the dicidol mixture C) is less than 10% by weight
  • the content of the metals chromium, nickel, copper, cadmium, lead and rhodium in the mixture of diclides C) is in each case less than 2 mg / kg, and
  • compositions are prepared by intensive mixing of the components at temperatures of 20 to 80 ° C ("Textbook of Lacktechnologie", Th. Brock, M. Groteklaes, P. Mischke, ed. V. Zorll, Vincentz Verlag, Hannover, 1998, Page 229 ff.)
  • Non-liquid components are optionally first dissolved in suitable solvents or water before mixing, then the remaining components are added with stirring, in the case of pigments and / or fillers, for example, dispersion takes place.
  • the subject matter is also the use of the coating material compositions.
  • C) is less than 2% by weight, the content of mono (hydroxymethyl) thcyclo [5.2.1.0 26 ] decane in the
  • Dicidol mixture C) is less than 10 wt .-%, - the content of the metals chromium, nickel, copper, cadmium, lead and
  • Each rhodium in the Dicidol mixture C) is less than 2 mg / kg, and
  • the coating compositions of the invention are used as aqueous, solvent-containing (normal, medium, high, very high solids) and / or solvent-free (powder and / or liquid) thermosetting, radiation-curable and / or air-drying (oxidatively and / or physically) sweeping agents, fillers -, sealants and / or adhesives.
  • the coating material compositions according to the invention can be used, in particular as solvent-containing and / or aqueous coating materials and / or as solvent-free coating materials (eg radiation-curable coating materials and / or powder coatings) such as fillers, primers, fillers, basecoats, topcoats and / or clearcoats, Printing inks, ballpoint pen pastes, Pigment preparations, inks, polishes, glazes, laminations, cosmetics, such. As nail polishes, sealants and insulating materials and adhesives.
  • solvent-containing and / or aqueous coating materials and / or as solvent-free coating materials eg radiation-curable coating materials and / or powder coatings
  • solvent-free coating materials eg radiation-curable coating materials and / or powder coatings
  • solvent-free coating materials eg radiation-curable coating materials and / or powder coatings
  • fillers e.g radiation-curable coating materials and / or powder coatings
  • primers e.g radiation-
  • substrates of z As metals, plastics, paper, cardboard, inorganic materials such. As ceramics, stone, concrete and / or glass, textiles, fibers, fabric materials, leather and synthetic materials, such as. B., imitation leather, wood, films of plastics and / or composites such. B. aluminum-laminated films with the invention
  • Coating material composition are coated.
  • the compositions can be used for all conceivable applications both indoors and outdoors, such. B. as Bautenschutzmaschine / -Iacke, road marking paints, automotive coatings (OEM, Refinish), coil coatings, can coatings, textile finishing, wood coatings, plastic coatings, and for decorative applications, etc. Also suitable for use in adhesives, such. As for the bonding of textiles, leather, paper, plastics, metals and similar materials, such compositions are suitable.
  • the coating materials of the invention can be applied by any known method, e.g. Rolling, brushing, dipping, flooding, spraying, pouring, rolling, spraying, printing, wiping, washing, tumbling, centrifuging.
  • the coating compositions of the invention are characterized by a high solids content.
  • the coating compositions according to the invention have a solids content of from 10% to 99.9%, preferably from 20% to 99.9%, particularly preferably from 50% to 99.9%.
  • the content of volatile organic compounds (VOC) is between 0 and 60 wt .-%, preferably between 0 and 40 wt .-%, particularly preferably between 0 and 30 wt .-%.
  • the dried, cured or crosslinked films which are obtained from the coating compositions according to the invention are distinguished by particularly good adhesion to metallic, mineral substrates or to substrates made of wood and plastics critical climatic conditions with high corrosion protection, a high gloss and a very good stone chip resistance and resistance to salt solutions.
  • the coating compositions according to the invention have very good adhesion properties to underlying coatings; Also, the intercoat adhesion to overlying layers is positively affected.
  • compositions of the invention have a high yellowing resistance and a very good hardness elasticity balance.
  • the invention also relates to objects coated with the coating material compositions.
  • the formaldehyde content is determined by the lutidine method by HPLC
  • HPLC system with two isocratic pumps, thermostatically controlled reactor, variable UVA / IS detector and evaluation unit, eg. B. Hewlett-Packard HP 1100 with
  • the benzene content was determined by headspace GC / FID analysis.
  • Carrier gas nitrogen column pre-pressure: 70 kPa high-pressure dosage: 150 kPa GC method: oven temperature: 50 0 C; 4 minutes; 57min - 130 0 C; 307min - 180 0 C; 10 min
  • Injector temperature 160 ° C
  • the content of the metals chromium, nickel, copper, cadmium, lead and rhodium was determined by means of atomic absorption spectroscopy (AAS).
  • Rh is measured by flame AAS (atomic absorption spectrometry, Varian SpectrAA 220FS, with acetylene / air flame). The meter is calibrated from 0 to 4 mg / L. NaHSO 4 is added as a matrix modifier to the measurement solution.
  • AAS atomic absorption spectrometry, Varian SpectrAA 220FS, with acetylene / air flame.
  • the meter is calibrated from 0 to 4 mg / L.
  • NaHSO 4 is added as a matrix modifier to the measurement solution.
  • the determination is carried out by mass spectroscopy by means of GC-MS.
  • the sample is analyzed by gas chromatography and then the detected components are identified by GC / MS analysis.
  • the quantification is carried out from the gas chromatogram by normalization to 100 areas%.
  • Injector temperature 275 ° C
  • the determination of aldehydes by FT IR spectroscopy is prepared on NaCl slices and recorded the FT IR spectrum. The absence of a carbonyl band in the range 1600 - 1800 cm "1 proves that no aldehydes are present.
  • Tg glass transition temperature
  • the determination is based on DIN EN ISO 2114 "Determination of the acid number”.
  • nfA Determination of the content of nonvolatile matter
  • the content of nonvolatile matter is determined in accordance with DIN EN ISO 3251. It is given as the mean value from a duplicate determination.
  • a cleaned aluminum dish (Taramasse nr ⁇ ) are weighed on an analytical balance about 2 g of the sample (mass m 2 of the substance). Subsequently, the aluminum dish is placed for 24 h at 160 ° C in a convection oven. The dish is cooled to room temperature and weighed to the nearest 0.1 mg (m 3 ).
  • the nonvolatile fraction (nfA) is calculated according to the following equation:
  • the Gardner color number is determined in 60% solution of the resin in
  • the color number after thermal stress is determined in this way.
  • the resin is first stored for 24 hours at 160 ° C. in an air atmosphere (see Determination of the non-volatile content).
  • the Gardner color number is then determined in 50% strength solution of the thermally stressed resin in xylene based on DIN EN ISO 4630.
  • the solution viscosity is determined according to DIN EN ISO 3219. If a solid resin is present, it is first dissolved in a suitable solvent, such as, for example, xylene, with a solids content of, for example, 60%. The viscosity is measured at 23 0 C using a plate / cone viscometer (1 / 4OS).
  • a suitable solvent such as, for example, xylene
  • the hardness was determined by means of pendulum damping (DIN EN ISO 1522), the elasticity by means of Erichsentiefung (DIN EN ISO 1520).
  • the measurement was carried out by determining the density of the formulation before (CI M ) and after UV curing (dp) by means of a gas pycnometer (Jeffrey Stansbury, Junhao Ge, RadTech Report, May / June 2003, p. 56-62):
  • polyesters were used as a 60% solution in xylene in a 1K alkyd melamine stoving lacquer.
  • the lacquers were mounted on aluminum sheets with a 100 .mu.m pull frame and cured at 140.degree. C. for 30 min.
  • the formulation is shown in Table 1.
  • the coated panels were then subjected to a weather-o-meter test.
  • the CIE-Lab color differences between the comparative film without polyester essential to the invention and the film with polyester essential to the invention were measured according to DIN 6174 / DIN 5033 with the measuring device x-rite 8200 spectrophotometer (measurement parameters: without gloss / aperture 12.7 mm / illuminant D65 / 10 °) determined.
  • a good Wetting is achieved when the applied paint a closed film without defects such.
  • a good course is achieved if the applied, closed film has a low intrinsic structure (eg, orange peel, too deep penetration into the substrate in, for example, woods, or the like).
  • the determination of the compatibility is carried out in such a way that the polyester essential to the invention 1 with the binder to be tested in a mass ratio of 1: 4 and 1: 2 (based on solid resin) dissolved in 50% solution in the solvent in which the resin to be tested is, is mixed. By optically assessing the solution, it is examined for turbidity and incompatibilities. After mounting the solutions on glass plates and evaporation of the solvent then the visual assessment of the film is carried out for turbidity and incompatibilities.
  • non-volatile fraction (nfA) is calculated according to the following equation: - 100 [mass%]
  • the content of tricyclodecane (mono- / di-) aldehyde in the Dicidolgemisch used was less than 2 wt .-%, the content of mono (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane was below 10 wt .-% and the content of Rhodium below 2 mg / kg.
  • the content of the metals chromium, nickel, copper, cadmium and lead was less than 1 mg / kg.
  • the content of benzene and the content of formaldehyde were below 10 mg / kg each.
  • the compatibility of the two inventive polyesters from Examples 1 and 2 were investigated. They have for example a good compatibility with PVC, chlorinated rubber, nitrocellulose, ketone-aldehyde resins, alkyd resins, acrylate resins, polyesters, melamine resins, urea resins and polyisocyanates.
  • the content of benzene and formaldehyde content in the compositions B1 and B2 was less than 10 mg / kg.
  • Substrate galvanized steel / layer thickness (dry): approx. 30 ⁇ m / drying: 24 h
  • polyesters according to Examples 1 and 2 in the form of their 60% strength solutions in xylene are used in each case in a white corrosion protection varnish based on chlorinated rubber (V2) (Table 5).
  • V2 chlorinated rubber
  • thermoplastic acrylate resin 2% by weight of the thermoplastic acrylate resin is replaced by the polyester of Example 2 in the form of its 60% solution in xylene (Table 11).
  • the originally bad fixation of the aluminum plates on ABS is optimized, the adhesion to ABS improved.
  • Substrate ABS Spray Viscosity: 20 seconds in the Ford 4 cup
  • Comparative Example C8 and Inventive Application Example B13 The aqueous polyester according to Example 3 was used in an aqueous plastic paint (V8). It significantly improves adhesion to EPDM.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Paper (AREA)

Abstract

La présente invention concerne des compositions de matière de revêtement destinées par ex. à des fonds métalliques minéraux ou à des fonds en bois, en papier et en matières plastiques, qui contiennent des polyesters amorphes, insaturés, faiblement visqueux, résistant au jaunissement qui sont dans une large mesure exempts de benzène et de formaldéhyde, ce qui permet d'améliorer l'adhérence de ces compositions de matière de revêtement même dans des conditions climatiques critiques. L'invention a également pour objet un procédé de préparation de ces compositions et leur utilisation.
PCT/EP2008/057370 2007-07-24 2008-06-12 Compositions de matière de revêtement WO2009013064A2 (fr)

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US9309438B2 (en) 2011-04-05 2016-04-12 ALLNEX Belgium SA Radiation curable compositions
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JP7513199B2 (ja) 2022-03-17 2024-07-09 三菱ケミカル株式会社 トリシクロデカンジメタノール組成物、紫外線硬化性組成物、重合体組成物、及びトリシクロデカンジメタノール組成物の製造方法

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