EP0787170A1 - Radiation-curable coatings based on lignin derivatives - Google Patents

Radiation-curable coatings based on lignin derivatives

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Publication number
EP0787170A1
EP0787170A1 EP95936463A EP95936463A EP0787170A1 EP 0787170 A1 EP0787170 A1 EP 0787170A1 EP 95936463 A EP95936463 A EP 95936463A EP 95936463 A EP95936463 A EP 95936463A EP 0787170 A1 EP0787170 A1 EP 0787170A1
Authority
EP
European Patent Office
Prior art keywords
lignin
meth
radiation
derivatives
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP95936463A
Other languages
German (de)
French (fr)
Inventor
Wolfgang Reich
Jörg Breitenbach
Harald Larbig
Erich Beck
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0787170A1 publication Critical patent/EP0787170A1/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C09D197/00—Coating compositions based on lignin-containing materials
    • C09D197/005—Lignin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • 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
    • C09D167/07—Unsaturated polyesters having carbon-to-carbon unsaturation having terminal carbon-to-carbon unsaturated bonds
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the invention relates to a method for producing coatings. It is generally known to use (meth) acrylates for the production of coatings.
  • (meth) acrylates for the production of coatings.
  • Mono- or poly (meth) acrylates such as alkyl (meth) acrylates, alkylene di-, tri- or tetra (meth) acrylates, urethane (meth) acrylates, epoxy (meth) acrylates, polyether or polyesters (meth) acrylates.
  • Lignin as a renewable raw material is known to be obtained from wood processing. For example, through implementation with
  • the object of the present invention was a process for the production of coatings in which all or part of the compounds used hitherto are replaced by those based on renewable raw materials, these compounds exhibiting good reactivity in the radiation curing and the cured coatings obtained should have satisfactory application properties. Accordingly, a process for the production of coatings has been found, in which radiation-curable compounds which contain at least 5% by weight, based on these compounds, of radically copolymerizable lignin derivatives are applied to substrates and cured.
  • radiation-curable i.e. Radically copolymerizable compounds applied to substrates.
  • Such radiation curable compounds are e.g. Compounds of the formula
  • X represents an n-valent C 1 -C 2 alkyl radical, which can optionally be substituted by 1 to 3 hydroxyl groups
  • R 1 represents an H atom or a methyl group and n has the meaning of an integer from 1 to 4 has.
  • Compounds of the formula I are, for example, -C 2 -C 8, preferably C 1 -C 6 alkyl (meth) acrylates, C 2 -C 10 -alkylenedi (meth) acrylates or trimethylolpropane mono-, di- or tri (meth) acrylate, Pentaerythritol mono-, di-, tri- or tetra (meth) acrylate.
  • the radiation-curable compounds can be polyester or polyether (meth) acrylates. Preferred are those obtained by reacting (meth) acrylic acid with 1 to 6, preferably 2 to 4 hydroxyl-containing polyesters or polyethers.
  • the molecular weights M n of the polyesters or polyethers are preferably between 100 and 4000.
  • Such hydroxyl-containing polyesters can be prepared, for example, in a customary manner by esterifying dicarboxylic acids or polycarboxylic acids with diols or polyols.
  • the starting materials for such hydroxyl-containing polyesters are known to the person skilled in the art.
  • Preferred dicarboxylic acids are succinic acid, glutaric acid, adipic acid, sebacic acid, o-phthalic acid, Acid, its isomers and hydrogenation products and esterifiable derivatives, such as anhydrides, for example maleic anhydride or dialkyl esters of the acids mentioned are used.
  • Tri- or tetraacids such as trimellitic anhydride or benzene tetracarboxylic acid may be mentioned as polycarbonic acid or its anhydrides.
  • Suitable diols are preferably ethylene glycol, propylene glycol 1,2 and 1,3, butane diol 1,4, hexane diol 1,6, neopentyl glycol, cyclohexane dimethanol and polyglycols of the ethylene glycol and propylene glycol type.
  • Trimethylolpropane, glycerol or pentaerythritol are primarily mentioned as polyols.
  • diols or polyols are oxyalkylated (e.g. with ethylene oxide or propylene oxide) diols or polyols, in particular with a degree of oxyalkylation of 0 to 10, based on the respective hydroxyl groups of the diol or polyol.
  • oxyalkylated diols or polyols in particular with a degree of oxyalkylation of 0 to 10, based on the respective hydroxyl groups of the diol or polyol.
  • polyesterols to be used according to the invention also include polycaprolactone diols and triols, the preparation of which is likewise known to the person skilled in the art.
  • hydroxyl-containing polyethers examples include those in question which can be obtained by known processes by reacting di- and / or polyhydric alcohols with different amounts of ethylene oxide and / or propylene oxide. Similarly, polymerization products of tetrahydrofuran or butylene oxide can also be used.
  • Oxalkylation products of the abovementioned diols or polyols are preferred, in particular with a degree of oxalkylation of 0 to 10, based on the respective hydroxyl groups of the diol or polyol, at least 2 ether groups being contained in the molecule.
  • Urethane (meth) acrylates such as are obtainable by reacting mono-isocyanates or polyisocyanates with (meth) acrylates containing hydroxyl groups, in particular also those of the formula I, are also used as radiation-curable compounds for the production of coatings.
  • polyisocyanates are aliphatic, cycloaliphatic and aromatic diisocyanates, for example 1,4-butanediisocyanate, 1,6-hexanediisocyanate, 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate, cyclohexanediisocyanate, methylcyclohexanedi isocyanate, isophorone diisocyanate, 4,4'-diisocyanatodiphenylmethane, 4,4'-diisocyanatodicyclohexylmethane, 2,4- and 2,6-tolylene diisocyanate, tetramethylxylylene diisocyanate.
  • 1,4-butanediisocyanate 1,6-hexanediisocyanate
  • 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate 2,2,4- and 2,4,4-trimethylhexamethylene diisocyan
  • epoxy (meth) acrylates may be mentioned, e.g. such as those obtained by reacting epoxidized olefins or diglycidyl ethers, e.g. aromatic polyepoxides, such as bisphenol A diglycidyl ether with (meth) acrylic acid are available.
  • the radiation-curable compounds used in the process according to the invention contain at least 5% by weight of radiation-curable, free-radically copolymerizable lignin derivatives, based on the total amount of the radiation-curable compounds.
  • the radiation-curable compounds can also be exclusively lignin derivatives.
  • Coatings with good hardness and good elasticity can e.g. are obtained if the radiation-curable compounds consist of 5 to 50, preferably 5 to 40% by weight of lignin derivatives.
  • Radiation-curable lignin derivatives are e.g. with allyl or
  • Corresponding lignin derivatives can e.g. are obtained by reacting lignin with (meth) acrylic acid chloride or (meth) acrylic anhydride, e.g. in Cellulose Chem. Technol. 9, 71-77 (1975).
  • lignin can be alkoxylated, in particular ethoxylated or propoxylated, by known processes.
  • the alkoxylated lignin can then easily be reacted with (meth) acrylic acid to give a radiation-curable lignin derivative.
  • Lignins which are alkoxylated on average with 0.5 to 10, particularly preferably with 1 to 5, alkoxy groups per hydroxyl group are preferably used here. These lignins can then be reacted with (meth) acrylic acid by conventional esterification processes. Because of their low viscosity, the lignin derivatives obtained in this way are particularly suitable for the process according to the invention.
  • Lignin can also be reacted with isocyanate compounds.
  • radiation-curable lignins can be obtained by reacting lignin with e.g. Isocyanato-alkyl (meth) acrylates are converted into radiation-curable derivatives.
  • lignin can e.g. also with poly-isocyanates and hydroxyalkyl (meth) acrylates, e.g. those of the formula I or the above-described polyether or polyester (meth) acrylates, which additionally carry at least one hydroxyl group, are converted into radiation-curable derivatives.
  • the radiation-curable lignin derivatives preferably have an average molecular weight M n of 500 to 5000 M n , in this case by gel chromatography with polystyrene as the standard and tetrahydrofuran as the eluent, as described in Am. Chem. Soc, Symp. Ser. 397 (1989), pages 100-108.
  • the radiation-curable lignin derivatives preferably contain 1 to 20% by weight, particularly preferably 2 to 10% by weight, very particularly preferably 3 to 6% by weight of the copolymerizable ethylenically unsaturated group>
  • C C ⁇ (based on the radiation-hardened group) - cash lignin derivatives).
  • the radiation-curable compounds are applied to substrate surfaces.
  • the radiation-curable compounds can also contain further additives, e.g. Film forming aids, thickeners, defoamers or dyes, fillers or pigments are added.
  • further additives e.g. Film forming aids, thickeners, defoamers or dyes, fillers or pigments are added.
  • solvents are also used if the radiation-curable compounds are solid or have too high a viscosity.
  • Suitable solvents are, for example, dioxane, butyl acetate, ethyl acetate, dimethylformamide, N-methylpyrrolidone, ketones such as methyl, ethyl ketone.
  • the application can be carried out by conventional methods such as brushing, knife coating of the syringes.
  • Suitable substrates are those made of metal, plastic, paper or wood. Wood and paper are preferred.
  • solvents if present, can be removed, for example by increasing the temperature, and then thermal or photochemical curing can be carried out, preferably at room temperature. Photochemical curing by irradiation with high-energy light, for example electron beams or UV light, is preferred.
  • the radiation-curable compounds used according to the invention show good reactivity with regard to radiation curing and result in scratch-resistant coatings even after a short exposure.
  • photoinitiators are suitably added to the radiation-curable compounds, preferably in amounts of 0.05 to 5% by weight, based on the radiation-curable compounds.
  • Possible photoinitiators are e.g. Benzophenone and derivatives thereof, e.g. Alkylbenzophenones, halogen-methylated benzophenones, Michler's ketone, as well as benzoin and benzoin ethers such as ethylbenzoin ether, benzil ketals such as benzil dimethyl ketal, acetophenone derivatives such as e.g. Hydroxy-2-methyl-l-phenylpropan-l-one and hydroxycyclohexyl-phenylketone, anthraquinone and its derivatives such as methylanthraquinone and especially acylphosphine oxides such as e.g. Lucirin® TPO (2, 4,6-trimethylbenzoyldiphenylphosphine oxide).
  • Benzophenone and derivatives thereof e.g. Alkylbenzophenones, halogen-methylated benzophenones, Michler's
  • the photoinitiators which, depending on the intended use of the compositions according to the invention, are used in amounts between 0.1 and 15% by weight, preferably 1 to 10% by weight, based on the polymerizable components, can be used as a single substance or, because of their more frequent use synergistic effects, can also be used in combination.
  • the cured coatings have good application properties, e.g. good hardness and flexibility.
  • Stabilizers and 1.8 g of sulfuric acid were added to acrylic acid and 76.6 g of methylcyclohexane, and the mixture was heated to 100.degree.
  • 13 ml of acrylic acid-containing water with an acid number of 322.2 mg KOH / g were removed (56.4% esterification).
  • the solvent and excess of acrylic acid to an acid number of 46.2 mgKOH / g was distilled off ⁇ .
  • 24.4 g of bisphenol A diglycidyl ether (Epikote® 828) and 8.0 g of tetrabutylammonium bromide were then added at 107 ° C. After a reaction time of 3 hours, the product was filtered and filled.
  • the product had one Acid number of 2 mg KOH / g substance and a viscosity of 1.9 Pas.
  • the resin was mixed with 4% Irgacure 500, mounted on a bonder sheet with a box squeegee (layer thickness 50 ⁇ m) and irradiated with 2 UV lamps of 80 watts each in air, the speed of the conveyor belt being 13 m / min (5 times irradiated).
  • the pendulum damping was determined according to DIN 53157, which is a measure of the hardness of a coating, and the Erichsen depression according to DIN ISO 1520, which is a measure of the flexibility, elasticity of a coating.

Abstract

A process for making coatings in which radiation-curable compounds containing at least 5 wt.% of radically copolymerised lignin derivatives in relation to said compounds are applied to substrates and cured.

Description

Strahlungshärtbare Beschichtungen auf Basis von igninderivatenRadiation-curable coatings based on ignition derivatives
Beschreibungdescription
Die Erfindung betrifft ein Verfahren zur Herstellung von Be¬ schichtungen. Es ist allgemein bekannt, (Meth)acrylate zur Her¬ stellung von Beschichtungen zu verwenden. In Betracht kommen da¬ bei z.B. Mono- oder Poly(meth)acrylate, wie Alkyl(meth)acrylate, Alkylendi-, -tri- oder -tetra(meth)acrylate, Ure- than(meth)acrylate, Epoxid(meth)acrylate, Polyether- oder Poly¬ ester(meth)acrylate.The invention relates to a method for producing coatings. It is generally known to use (meth) acrylates for the production of coatings. For example, Mono- or poly (meth) acrylates, such as alkyl (meth) acrylates, alkylene di-, tri- or tetra (meth) acrylates, urethane (meth) acrylates, epoxy (meth) acrylates, polyether or polyesters (meth) acrylates.
Neben dieser Vielzahl synthetischer Verbindungen sind Verbindungen auf Basis nachwachsender Rohstoffe bisher kaum zur Herstellung von Beschichtungen verwendet worden.In addition to this multitude of synthetic compounds, compounds based on renewable raw materials have so far hardly been used for the production of coatings.
Es besteht jedoch zunehmend Nachfrage nach neuen, preisgünstigen Rohstoffen für Beschichtungen, welche auch vorteilhaft in Hin- sieht auf ihre Umweltverträglichkeit und ihre Recyclebarkeit, bzw. der Recyclebarkeit der beschichteten Substrate sein sollen.However, there is an increasing demand for new, inexpensive raw materials for coatings, which should also be advantageous in terms of their environmental compatibility and their recyclability or the recyclability of the coated substrates.
Zur Herstellung von strahlungshärtbaren Beschichtungen verwendete Verbindungen sollen gleichzeitig eine möglichst gute Reaktivität bezüglich der Strahlungshärtung zeigen und nach erfolgter Strah¬ lungshärtung Beschichtungen mit guten anwendungstechnischen Ei¬ genschaften ergeben.Compounds used to produce radiation-curable coatings should at the same time show the best possible reactivity with regard to radiation curing and, after radiation curing, should result in coatings with good application properties.
Lignin als nachwachsender Rohstoff wird bekanntlich bei der Holz- Verarbeitung gewonnen. Es kann z.B. durch Umsetzung mitLignin as a renewable raw material is known to be obtained from wood processing. For example, through implementation with
(Meth)acrylsäurechlorid oder -anhydrid modifiziert und dann als Comonomer mit anderen Monomeren, z.B. Methylmethacrylat, copoly- merisiert werden (Cellulose Chem. Techno1. 9, 71-77 (1975).Modified (meth) acrylic acid chloride or anhydride and then as a comonomer with other monomers, e.g. Methyl methacrylate, are copolymerized (Cellulose Chem. Techno 1.9, 71-77 (1975).
Des weiteren ist z.B. bekannt, Lignin mit Isocyanatoethylmeth- acrylat umzusetzen.Furthermore, e.g. known to implement lignin with isocyanatoethyl methacrylate.
Aufgabe der vorliegenden Erfindung war ein Verfahren zur Herstel¬ lung von Beschichtungen, bei dem die bisher verwendeten Verbindungen ganz oder teilweise durch solche auf Basis nachwach¬ sender Rohstoffe ersetzt werden, wobei diese Verbindungen bei der Strahlungshärtung eine gute Reaktivität zeigen und die erhaltenen, gehärteten Beschichtungen zufriedenstellende anwendungstechnische Eigenschaften aufweisen sollen. Demgemäß wurde ein Verfahren zur Herstellung von Beschichtungen, wobei man strahlungshärtbare Verbindungen, welche zu mindestens 5 Gew. -%, bezogen auf diese Verbindungen, radikalisch copoly- merisierbare Ligninderivate enthalten, auf Substrate aufträgt und härtet, gefunden.The object of the present invention was a process for the production of coatings in which all or part of the compounds used hitherto are replaced by those based on renewable raw materials, these compounds exhibiting good reactivity in the radiation curing and the cured coatings obtained should have satisfactory application properties. Accordingly, a process for the production of coatings has been found, in which radiation-curable compounds which contain at least 5% by weight, based on these compounds, of radically copolymerizable lignin derivatives are applied to substrates and cured.
Gefunden wurden auch Beschichtungen, welche nach einem solchen Verfahren erhältlich sind.Coatings which can be obtained by such a process were also found.
Bei dem erfindungsgemäßen Verfahren werden strahlungshärtbare d.h. radikalisch copolymerisierbare Verbindungen auf Substrate aufgetragen.In the method according to the invention, radiation-curable i.e. Radically copolymerizable compounds applied to substrates.
Solche strahlungshärtbaren Verbindungen sind z.B. Verbindungen der FormelSuch radiation curable compounds are e.g. Compounds of the formula
00
X(-0-C-CH=CH2)n IX (-0-C-CH = CH 2 ) n I
R1 R 1
worin X für einen n-wertigen Cι-C2o Alkylrest, welcher gegebenen¬ falls durch 1 bis 3 Hydroxygruppen substituiert sein kann, steht, R1 für ein H-Atom oder eine Methylgruppe steht und n die Bedeutung einer ganzen Zahl von 1 bis 4 hat.in which X represents an n-valent C 1 -C 2 alkyl radical, which can optionally be substituted by 1 to 3 hydroxyl groups, R 1 represents an H atom or a methyl group and n has the meaning of an integer from 1 to 4 has.
Verbindungen der Formel I sind z.B. Cι-C2o-, vorzugsweise Ci-Cβ-Alkyl (meth)acrylate, C2-Cι0-Alkylendi(meth)acrylate oder Trimethylolpropanmono- , -di- oder -tri (meth)acrylat, Penta- erythritmono- , -di-, -tri- oder tetra(meth)acrylat.Compounds of the formula I are, for example, -C 2 -C 8, preferably C 1 -C 6 alkyl (meth) acrylates, C 2 -C 10 -alkylenedi (meth) acrylates or trimethylolpropane mono-, di- or tri (meth) acrylate, Pentaerythritol mono-, di-, tri- or tetra (meth) acrylate.
Weiterhin kann es sich bei den strahlungshärtbaren Verbindungen um Polyester- oder Polyether(meth)acrylate handeln. Bevorzugt sind dabei solche, wie sie durch Umsetzung von (Meth)acrylsäure mit 1 bis 6, vorzugsweise 2 bis 4 Hydroxylgruppen enthaltenden Polyestern oder Polyethern erhältlich sind.Furthermore, the radiation-curable compounds can be polyester or polyether (meth) acrylates. Preferred are those obtained by reacting (meth) acrylic acid with 1 to 6, preferably 2 to 4 hydroxyl-containing polyesters or polyethers.
Die Molekulargewichte Mn der Polyester bzw. Polyether liegen bevorzugt zwischen 100 und 4000.The molecular weights M n of the polyesters or polyethers are preferably between 100 and 4000.
Derartige hydroxylgruppenhaltige Polyester können z.B. in üblicher Weise durch Veresterung von Dicarbonsäuren oder Poly- carbonsäuren mit Diolen oder Polyolen hergestellt werden. Die Ausgangsstoffe für solche hydroxylgruppenhaltige Polyester sind dem Fachmann bekannt. Bevorzugt können als Dicarbonsäuren Bernsteinsäure, Glutarsäure, Adipinsäure, Sebacinsäure, o-Phthal- säure, deren Isomere und Hydrierungsprodukte sowie veresterbare Derivate, wie Anhydride, z.B. Maleinsäureanhydrid oder Dialkyl- ester der genannten Säuren eingesetzt werden. Als Polycarbon- säure, bzw. deren Anhydride seien Tri- oder Tetrasäuren wie Tri- mellitsäureanhydrid oder Benzoltetracarbonsäure genannt. Als Diole kommen vorzugsweise in Betracht Ethylenglykol, Propylen- glykol-1,2 und -1,3, Butandiol-1,4, Hexandiol-1,6, Neopentyl- glykol, Cyclohexandimethanol sowie Polyglykole vom Typ des Ethylenglykols und Propylenglykols.Such hydroxyl-containing polyesters can be prepared, for example, in a customary manner by esterifying dicarboxylic acids or polycarboxylic acids with diols or polyols. The starting materials for such hydroxyl-containing polyesters are known to the person skilled in the art. Preferred dicarboxylic acids are succinic acid, glutaric acid, adipic acid, sebacic acid, o-phthalic acid, Acid, its isomers and hydrogenation products and esterifiable derivatives, such as anhydrides, for example maleic anhydride or dialkyl esters of the acids mentioned are used. Tri- or tetraacids such as trimellitic anhydride or benzene tetracarboxylic acid may be mentioned as polycarbonic acid or its anhydrides. Suitable diols are preferably ethylene glycol, propylene glycol 1,2 and 1,3, butane diol 1,4, hexane diol 1,6, neopentyl glycol, cyclohexane dimethanol and polyglycols of the ethylene glycol and propylene glycol type.
Als Polyole sind in erster Linie Trimethylolpropan, Glycerin oder Pentaerythrit zu nennen.Trimethylolpropane, glycerol or pentaerythritol are primarily mentioned as polyols.
Als Diole oder Polyole in Betracht kommen auch oxalkylierte (z.B. mit Ethylenoxid oder Propylenoxid) Diole oder Polyole, insbesondere mit einem Oxalkylierungsgrad von 0 bis 10, bezogen auf die jeweiligen Hydroxygruppen des Diols oder Polyols.Also suitable as diols or polyols are oxyalkylated (e.g. with ethylene oxide or propylene oxide) diols or polyols, in particular with a degree of oxyalkylation of 0 to 10, based on the respective hydroxyl groups of the diol or polyol.
Zu den erfindungsgemäß einzusetzenden Polyesterolen zählen auch Polycaprolactondiole und -triole, deren Herstellung dem Fachmann ebenfalls bekannt ist.The polyesterols to be used according to the invention also include polycaprolactone diols and triols, the preparation of which is likewise known to the person skilled in the art.
Als hydroxylgruppenhaltige Polyether kommen z.B. solche in Frage, welche nach bekannten Verfahren durch Umsetzung von zwei- und/oder mehrwertigen Alkoholen mit verschiedenen Mengen an Ethylenoxid und/oder Propylenoxid erhalten werden können. Des¬ gleichen sind auch Polymerisationsprodukte des Tetrahydrofurans oder Butylenoxids verwendbar.Examples of hydroxyl-containing polyethers include those in question which can be obtained by known processes by reacting di- and / or polyhydric alcohols with different amounts of ethylene oxide and / or propylene oxide. Similarly, polymerization products of tetrahydrofuran or butylene oxide can also be used.
Bevorzugt sind Oxalkylierungsprodukte der obengeannten Diole oder Polyole, insbesondere mit einem Oxalkylierungsgrad von 0 bis 10, bezogen auf die jeweiligen Hydroxylgruppen des Diols oder Polyols, wobei mindestens 2 Ethergruppen im Molekül enthalten sind.Oxalkylation products of the abovementioned diols or polyols are preferred, in particular with a degree of oxalkylation of 0 to 10, based on the respective hydroxyl groups of the diol or polyol, at least 2 ether groups being contained in the molecule.
Urethan(meth)acrylate, wie sie durch Umsetzung von Mono-isocyana- ten oder Polyisocyanaten mit Hydroxylgruppen enthaltenden (Meth) acrylaten, insbesondere auch solchen der Formel I, erhält¬ lich sind, werden ebenfalls als strahlungshärtbare Verbindungen zur Herstellung von Beschichtungen verwendet.Urethane (meth) acrylates, such as are obtainable by reacting mono-isocyanates or polyisocyanates with (meth) acrylates containing hydroxyl groups, in particular also those of the formula I, are also used as radiation-curable compounds for the production of coatings.
Als Polyisocyanate zu nennen sind z.B. aliphatische, cycloali- phatische und aromatische Diisocyanate, z.B. 1, 4-Butandiiso- cyanat, 1,6-Hexandiisocyanat, 2,2,4- und 2,4,4-Trimethylhexa- methylendiisocyanat, Cyclohexandiisocyanat, Methylcyclohexandi- isocyanat, Isophorondiisocyanat, 4,4' -Diisocyanatodiphenylmethan, 4, 4' -Diisocyanatodicyclohexylmethan, 2,4- und 2 , 6-Toluylendiiso- cyanat, Tetramethylxylylendiisocyanat.Examples of polyisocyanates are aliphatic, cycloaliphatic and aromatic diisocyanates, for example 1,4-butanediisocyanate, 1,6-hexanediisocyanate, 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate, cyclohexanediisocyanate, methylcyclohexanedi isocyanate, isophorone diisocyanate, 4,4'-diisocyanatodiphenylmethane, 4,4'-diisocyanatodicyclohexylmethane, 2,4- and 2,6-tolylene diisocyanate, tetramethylxylylene diisocyanate.
Gut geeignet sind auch die Uretdion-, Biuret- und Isocyanurat- Gruppen aufweisenden Additionsprodukte insbesondere der Diiso- cyanate.The addition products containing uretdione, biuret and isocyanurate groups, in particular diisocyanates, are also very suitable.
Schließlich seien noch Epoxid(meth)acrylate genannt, z.B. solche wie sie durch Umsetzung von epoxidierten Olefinen oder Diglycidy- lethern, z.B. aromatischen Polyepoxiden, wie Bisphenol-A-diglyci- dylether mit (Meth)acrylsäure erhältlich sind.Finally, epoxy (meth) acrylates may be mentioned, e.g. such as those obtained by reacting epoxidized olefins or diglycidyl ethers, e.g. aromatic polyepoxides, such as bisphenol A diglycidyl ether with (meth) acrylic acid are available.
Die in dem erfindungsgemäßen Verfahren verwendeten strahlungs- härtbaren Verbindungen enthalten mindestens 5 Gew. -%, strahlungs- härtbare, radikalisch copolymerisierbare Ligninderivate, bezogen auf die Gesamtmenge der strahlungshärtbaren Verbindungen. Bei den strahlungshärtbaren Verbindungen kann es sich auch ausschließlich um Ligninderivate handeln.The radiation-curable compounds used in the process according to the invention contain at least 5% by weight of radiation-curable, free-radically copolymerizable lignin derivatives, based on the total amount of the radiation-curable compounds. The radiation-curable compounds can also be exclusively lignin derivatives.
Beschichtungen mit guter Härte und guter Elastizität können z.B. erhalten werden, wenn die strahlungshärtbaren Verbindungen zu 5 bis 50, vorzugsweise 5 bis 40 Gew. -% aus Ligninderivaten beste¬ hen.Coatings with good hardness and good elasticity can e.g. are obtained if the radiation-curable compounds consist of 5 to 50, preferably 5 to 40% by weight of lignin derivatives.
Strahlungshärtbare Ligninderivate sind z.B. mit Allyl- oderRadiation-curable lignin derivatives are e.g. with allyl or
0 II Vinyl- insbesondere mit Acrylgruppen H2C-C-C-0- modifizierte0 II vinyl - especially modified with acrylic groups H 2 CCC-0
Ri Lignine (R1=H oder Methyl) .Ri lignins (R 1 = H or methyl).
Entsprechende Ligninderivate können z.B. erhalten werden durch Umsetzung von Lignin mit (Meth)acrylsäurechlorid oder (Meth)acrylsäureanhydrid, wie es z.B. in Cellulose Chem. Technol. 9, 71-77 (1975) beschrieben ist.Corresponding lignin derivatives can e.g. are obtained by reacting lignin with (meth) acrylic acid chloride or (meth) acrylic anhydride, e.g. in Cellulose Chem. Technol. 9, 71-77 (1975).
Zur Verbesserung seiner Reaktivität, z.B. gegenüber (Meth)acryl- säure, kann Lignin nach bekannten Verfahren alkoxyliert, ins¬ besondere ethoxyliert oder propoxyliert, werden. Das alkoxylierte Lignin kann dann leicht mit (Meth)acrylsäure zu einem strahlungs¬ härtbaren Ligninderivat umgesetzt werden.To improve its reactivity, e.g. compared to (meth) acrylic acid, lignin can be alkoxylated, in particular ethoxylated or propoxylated, by known processes. The alkoxylated lignin can then easily be reacted with (meth) acrylic acid to give a radiation-curable lignin derivative.
Bevorzugt werden hierbei Lignine verwendet, welche im Mittel mit 0,5 bis 10, besonders bevorzugt mit 1 bis 5 Alkoxygruppen pro Hy¬ droxylgruppe alkoxyliert sind. Diese Lignine können dann nach üb¬ lichen Verfahren der Veresterung mit (Meth)acrylsäure umgesetzt werden. Die so erhaltenen Ligninderivate eignen sich aufgrund ihrer ge¬ ringen Viskosität besonders gut für das erfindungsgemäße Verfah¬ ren.Lignins which are alkoxylated on average with 0.5 to 10, particularly preferably with 1 to 5, alkoxy groups per hydroxyl group are preferably used here. These lignins can then be reacted with (meth) acrylic acid by conventional esterification processes. Because of their low viscosity, the lignin derivatives obtained in this way are particularly suitable for the process according to the invention.
Lignin kann auch mit IsocyanatVerbindungen umgesetzt werden.Lignin can also be reacted with isocyanate compounds.
So können strahlungshärtbare Lignine durch Reaktion von Lignin mit z.B. Isocyanato-alkyl(meth)acrylaten in strahlungshärtbare Derivate überführt werden. Lignin kann aber z.B. auch mit Poly- isocyanaten und Hydroxyalkyl (meth)acrylaten, z.B. solche der For¬ mel I oder voranstehend beschriebenen Polyether- oder Poly¬ ester(meth)acrylaten, welche zusätzlich mindestens eine Hydroxyl¬ gruppe tragen, zu strahlungshärtbaren Derivaten umgesetzt werden.For example, radiation-curable lignins can be obtained by reacting lignin with e.g. Isocyanato-alkyl (meth) acrylates are converted into radiation-curable derivatives. However, lignin can e.g. also with poly-isocyanates and hydroxyalkyl (meth) acrylates, e.g. those of the formula I or the above-described polyether or polyester (meth) acrylates, which additionally carry at least one hydroxyl group, are converted into radiation-curable derivatives.
Die strahlungshärtbaren Ligninderivate haben vorzugsweise ein mittleres Molekulargewicht Mn von 500 bis 5000Mn wird hierbei durch Gelper eationschromatographie mit Polystyrol als Standard und Tetrahydrofuran als Elutionsmittel, wie es in Am. Chem. Soc, Symp. Ser. 397 (1989), Seite 100 bis 108 beschrieben ist.The radiation-curable lignin derivatives preferably have an average molecular weight M n of 500 to 5000 M n , in this case by gel chromatography with polystyrene as the standard and tetrahydrofuran as the eluent, as described in Am. Chem. Soc, Symp. Ser. 397 (1989), pages 100-108.
Die strahlungshärtbaren Ligninderivate enthalten vorzugsweise 1 - 20 Gew.-%, besonders bevorzugt 2 bis 10 Gew. -%, ganz beson¬ ders bevorzugt 3 bis 6 Gew.-% der copolymerisierbaren ethylenisch ungesättigten Gruppe >C=C< (bezogen auf die strahlungshärt- baren Ligninderivate) .The radiation-curable lignin derivatives preferably contain 1 to 20% by weight, particularly preferably 2 to 10% by weight, very particularly preferably 3 to 6% by weight of the copolymerizable ethylenically unsaturated group> C = C <(based on the radiation-hardened group) - cash lignin derivatives).
Nach dem erfindungsgemäßen Verfahren werden die strahlungshärt¬ baren Verbindungen auf Substratoberflächen aufgetragen.In the process according to the invention, the radiation-curable compounds are applied to substrate surfaces.
Den strahlungshärtbaren Verbindungen können noch weitere Zusatz¬ stoffe, z.B. Filmbildehilfsmittel, Verdicker, Entschäumer oder Farbstoffe, Füllstoffe oder Pigmente zugesetzt werden.The radiation-curable compounds can also contain further additives, e.g. Film forming aids, thickeners, defoamers or dyes, fillers or pigments are added.
Insbesondere werden auch Lösungsmittel verwendet, wenn die strahlungshärtbaren Verbindungen fest sind oder eine zu hohe Vis¬ kosität aufweisen. Geeignete Lösungsmittel sind zum Beispiel Dioxan, Butylacetat, Ethylacetat, Dimethylformamid, N-Methylpyr- rolidon, Ketone wie Methyl-, Ethylketon.In particular, solvents are also used if the radiation-curable compounds are solid or have too high a viscosity. Suitable solvents are, for example, dioxane, butyl acetate, ethyl acetate, dimethylformamide, N-methylpyrrolidone, ketones such as methyl, ethyl ketone.
Die Auftragung kann durch übliche Methoden wie Streichen, Rakeln der Spritzen erfolgen.The application can be carried out by conventional methods such as brushing, knife coating of the syringes.
Geeignete Substrate sind solche aus Metall, Kunststoff, Papier oder Holz. Bevorzugt ist Holz und Papier. Nach der Auftragung kann Lösemittel, soweit vorhanden, z.B. durch Temperaturerhöhung entfernt werden und dann eine thermische oder photochemische Härtung vorzugsweise bei Raumtemperatur vorgenom¬ men werden. Bevorzugt ist eine photochemische Härtung durch Be- strahlen mit energiereichem Licht, z.B. Elektronenstrahlen oder UV-Licht. Die erfindungsgemäß eingesetzten strahlungshärtbaren Verbindungen zeigen eine gute Reaktivität bezüglich der Strah¬ lungshärtung und ergeben schon nach kurzer Bestrahlung kratzfeste Beschichtungen.Suitable substrates are those made of metal, plastic, paper or wood. Wood and paper are preferred. After the application, solvents, if present, can be removed, for example by increasing the temperature, and then thermal or photochemical curing can be carried out, preferably at room temperature. Photochemical curing by irradiation with high-energy light, for example electron beams or UV light, is preferred. The radiation-curable compounds used according to the invention show good reactivity with regard to radiation curing and result in scratch-resistant coatings even after a short exposure.
Bei der Härtung mit UV-Licht werden den strahlungshärtbaren Verbindungen geeigneterweise Photoinitiatoren, vorzugsweise in Mengen von 0,05 bis 5 Gew.-%, bezogen auf die strahlungshärtbaren Verbindungen zugesetzt.When curing with UV light, photoinitiators are suitably added to the radiation-curable compounds, preferably in amounts of 0.05 to 5% by weight, based on the radiation-curable compounds.
Als Photoinitiatoren in Betracht kommen z.B. Benzophenon und Derivate davon, wie z.B. Alkylbenzophenone, halogenmethylierte Benzophenone, Michlers Keton, sowie Benzoin und Benzoinether wie Ethylbenzoinether, Benzilketale wie Benzildimethylketal, Aceto- phenonderivate wie z.B. Hydroxy-2-methyl-l-phenylpropan-l-on und Hydroxycyclohexyl-phenylketon, Anthrachinon und seine Derivate wie Methylanthrachinon und insbesondere Acylphosphinoxide wie z.B. Lucirin® TPO (2, 4,6-Trimethylbenzoyldiphenylphosphinoxid) .Possible photoinitiators are e.g. Benzophenone and derivatives thereof, e.g. Alkylbenzophenones, halogen-methylated benzophenones, Michler's ketone, as well as benzoin and benzoin ethers such as ethylbenzoin ether, benzil ketals such as benzil dimethyl ketal, acetophenone derivatives such as e.g. Hydroxy-2-methyl-l-phenylpropan-l-one and hydroxycyclohexyl-phenylketone, anthraquinone and its derivatives such as methylanthraquinone and especially acylphosphine oxides such as e.g. Lucirin® TPO (2, 4,6-trimethylbenzoyldiphenylphosphine oxide).
Die Photoinitiatoren, die je nach Verwendungszweck der erfindungsgemäßen Massen in Mengen zwischen 0,1 und 15 Gew. -%, vorzugsweise 1 bis 10 Gew. -%, bezogen auf die polymerisierbaren Komponenten, eingesetzt werden, können als einzelne Substanz oder, wegen häufiger vorteilhafter synergistischer Effekte, auch in Kombination miteinander verwendet werden.The photoinitiators, which, depending on the intended use of the compositions according to the invention, are used in amounts between 0.1 and 15% by weight, preferably 1 to 10% by weight, based on the polymerizable components, can be used as a single substance or, because of their more frequent use synergistic effects, can also be used in combination.
Die gehärteten Beschichtungen weisen gute anwendungstechnische Eigenschaften, z.B. eine gute Härte und Flexibilität auf.The cured coatings have good application properties, e.g. good hardness and flexibility.
Beispielexample
107,9 g propoxyliertes Lignin (OH-Zahl 390 mgKOH/g) , 70,2 g107.9 g propoxylated lignin (OH number 390 mgKOH / g), 70.2 g
Acrylsäure und 76,6 g Methylcyclohexan wurden mit Stabilisa¬ toren und 1,8 g Schwefelsäure versetzt und auf 100°C aufge- heizt. Innerhalb von 14 Stunden wurden 13 ml acrylsäurehalti- ges Wasser mit einer Säurezahl von 322,2 mg KOH/g ausgekreist (56,4 % Veresterung). Das Lösungsmittel und überschüssige Acrylsäure wurden bis zu einer Säurezahl von 46,2 mgKOH/g ab¬ destilliert. Anschließend wurden bei 107°C 24,4 g Bisphenol- A-diglycidether (Epikote® 828) und 8,0 g Tetrabutylammonium- bromid zugegeben. Nach 3 Stunden Nachreaktion wurde das Produkt filtriert und abgefüllt. Das Produkt hatte eine Säurezahl von 2 mg KOH/g Substanz und eine Viskosität von 1,9 Pas.Stabilizers and 1.8 g of sulfuric acid were added to acrylic acid and 76.6 g of methylcyclohexane, and the mixture was heated to 100.degree. Within 14 hours, 13 ml of acrylic acid-containing water with an acid number of 322.2 mg KOH / g were removed (56.4% esterification). The solvent and excess of acrylic acid to an acid number of 46.2 mgKOH / g was distilled off ¬. 24.4 g of bisphenol A diglycidyl ether (Epikote® 828) and 8.0 g of tetrabutylammonium bromide were then added at 107 ° C. After a reaction time of 3 hours, the product was filtered and filled. The product had one Acid number of 2 mg KOH / g substance and a viscosity of 1.9 Pas.
Lackprüfung:Paint test:
a) rein:a) pure:
Das Harz wurde mit 4 % Irgacure 500 versetzt, mit einem Kastenrakel auf Bonderblech aufgezogen (Schichtdicke 50 μm) und mit 2 UV-Lampen zu je 80 Watt unter Luft be¬ strahlt, wobei die Geschwindigkeit des Transportbandes 13 m/min betrug (5 mal bestrahlt) .The resin was mixed with 4% Irgacure 500, mounted on a bonder sheet with a box squeegee (layer thickness 50 μm) and irradiated with 2 UV lamps of 80 watts each in air, the speed of the conveyor belt being 13 m / min (5 times irradiated).
(Ergebnisse in Tabelle 1)(Results in Table 1)
b) Abmischungen mit einem Oligoethertriacrylat (Laromer- ® 8863)b) Mixtures with an oligoether triacrylate (Laromer- ® 8863)
Mischungen des oben hergestellten Ligninderivats mit La¬ romer (LR) 8863 wurden wie unter a) mit Irgacure versetzt und bestrahlt (Prüfungsergebnisse in Tabelle 1) .Mixtures of the lignin derivative prepared above with laomer (LR) 8863 were treated with Irgacure as in a) and irradiated (test results in Table 1).
Bestimmt wurde die Pendeldämpfung nach DIN 53157, welche ein Maß für die Härte einer Beschichtung ist, und die Erichsentiefung nach DIN ISO 1520, welche ein Maß für die Flexibilität, Elastizität einer Beschichtung ist.The pendulum damping was determined according to DIN 53157, which is a measure of the hardness of a coating, and the Erichsen depression according to DIN ISO 1520, which is a measure of the flexibility, elasticity of a coating.
Tabelle 1: PrüfergebnisseTable 1: Test results
Gew. -Teile Gew. -Teile Pendeldämp- Erichsen¬ Ligninderivat LR 8863 fung tiefungParts by weight parts by pendulum damping Erichsen lignin derivative LR 8863 fung deepening
[S] [mm][S] [mm]
- 10 156 0,6- 10 156 0.6
1 9 143 0,81 9 143 0.8
3 7 131 1,93 7 131 1.9
5 5 78 2,95 5 78 2.9
7 3 48 57 3 48 5
10 - 39 5,4 10 - 39 5.4

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von Beschichtungen, dadurch gekennzeichnet, daß strahlungshärtbare Verbindungen, welche zu mindestens 5 Gew. -%, bezogen auf diese Verbindungen, radikalisch copolymerisierbare Ligninderivate enthalten, auf Substrate aufgetragen und gehärtet werden.1. Process for the production of coatings, characterized in that radiation-curable compounds which contain at least 5% by weight, based on these compounds, of radically copolymerizable lignin derivatives are applied to substrates and cured.
2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß die Härtung durch Bestrahlung mit energiereichem Licht erfolgt.2. The method according to claim 1, characterized in that the curing is carried out by irradiation with high-energy light.
3. Verfahren gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, daß es sich bei den Ligninderivaten um mit Acrylgruppen modifizierte Ligninderivate handelt.3. The method according to claim 1 or 2, characterized in that the lignin derivatives are lignin derivatives modified with acrylic groups.
4. Verfahren gemäß einem der Ansprüche 1 bis 3, dadurch gekenn¬ zeichnet, daß die mit Acrylgruppen modifizierten Lignin¬ derivate durch Umsetzung von alkoxyliertem Lignin mit (Meth)acrylsäure, von Lignin mit (Meth)acrylsäurechlorid oder (Meth)acrylsäureanhydrid, von Lignin mit Isocyanato- alkyl(meth)acrylaten oder von Lignin mit Polyisocyanaten und Hydroxyl- oder A inogruppen enthaltenden Mono- oder Poly(meth)acrylaten erhalten werden.4. The method according to any one of claims 1 to 3, characterized gekenn¬ characterized in that the modified with acrylic groups Lignin¬ derivatives by reaction of alkoxylated lignin with (meth) acrylic acid, of lignin with (meth) acrylic acid chloride or (meth) acrylic anhydride, of lignin with isocyanato-alkyl (meth) acrylates or of lignin with polyisocyanates and hydroxyl or amino groups-containing mono- or poly (meth) acrylates.
5. Verfahren gemäß einem der Ansprüche 1 bis 4, dadurch gekenn¬ zeichnet, daß die strahlungshärtbaren Verbindungen zu 5 bis 40 Gew.-% aus radikalisch copolymerisierbaren Ligninderivaten bestehen.5. The method according to any one of claims 1 to 4, characterized gekenn¬ characterized in that the radiation-curable compounds to 5 to 40 wt .-% consist of radically copolymerizable lignin derivatives.
6. Verfahren gemäß einem der Ansprüche 1 bis 5, zur Beschichtung von Holzoberflächen.6. The method according to any one of claims 1 to 5, for coating wooden surfaces.
7. Ligninderivate, erhältlich durch Umsetzung von alkoxyliertem Lignin mit (Meth)acrylsäure.7. Lignin derivatives, obtainable by reacting alkoxylated lignin with (meth) acrylic acid.
8. Beschichtungen, erhältlich nach einem Verfahren gemäß den An¬ sprüchen 1 bis 6. 8. Coatings obtainable by a process according to claims 1 to 6.
EP95936463A 1994-10-21 1995-10-10 Radiation-curable coatings based on lignin derivatives Withdrawn EP0787170A1 (en)

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DE4437720A DE4437720A1 (en) 1994-10-21 1994-10-21 Radiation-curable coatings based on lignin derivatives
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US20150197667A1 (en) 2014-01-15 2015-07-16 Ppg Industries Ohio, Inc. Polyester polymers comprising lignin
SE539828C2 (en) 2016-04-29 2017-12-12 Innventia Ab Lignin-containing sealant and / or coating compositions from renewable sources
EP3409727A1 (en) 2017-05-29 2018-12-05 Annikki GmbH Method for the preparation of a lignin prepolymer

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US3672817A (en) * 1970-12-14 1972-06-27 Westvaco Corp Alkylene chlorohydrin,oxide or carbonate modified sulfonated lignins in a disperse or vat dye cake
US4017430A (en) * 1975-06-23 1977-04-12 Georgia-Pacific Corporation Coating composition
US4339366A (en) * 1980-11-17 1982-07-13 Blount David H Process for the production of polyester resins
US4871825A (en) * 1987-10-28 1989-10-03 Reed Lignin Inc. Binder composed of a graft copolymer of high molecular weight lignin material and an acrylic monomer

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