WO2005014679A1 - Composes d'acrylate d'urethane a durcissement induit par la lumiere - Google Patents

Composes d'acrylate d'urethane a durcissement induit par la lumiere Download PDF

Info

Publication number
WO2005014679A1
WO2005014679A1 PCT/GB2003/003239 GB0303239W WO2005014679A1 WO 2005014679 A1 WO2005014679 A1 WO 2005014679A1 GB 0303239 W GB0303239 W GB 0303239W WO 2005014679 A1 WO2005014679 A1 WO 2005014679A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
group
groups
compound
residue
Prior art date
Application number
PCT/GB2003/003239
Other languages
English (en)
Inventor
Zlatan Batalovic
Branko Dunjic
Srba Tasic
Branislav Bozic
Enis Dzunuzovic
Radomir Saicic
Radomir Matovic
Original Assignee
Duga Uk Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Duga Uk Ltd filed Critical Duga Uk Ltd
Priority to AU2003251350A priority Critical patent/AU2003251350A1/en
Priority to PCT/GB2003/003239 priority patent/WO2005014679A1/fr
Publication of WO2005014679A1 publication Critical patent/WO2005014679A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
    • C08G18/4607—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen having halogens
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • 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
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/061—Polyesters; Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4286—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones prepared from a combination of hydroxycarboxylic acids and/or lactones with polycarboxylic acids or ester forming derivatives thereof and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
    • C08G18/4676—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing sulfur
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • 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
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/005—Hyperbranched macromolecules
    • C08G83/006—After treatment of hyperbranched macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/066—Copolymers with monomers not covered by C08L33/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Definitions

  • This invention relates to photo-curable urethane-acrylate compounds, more particularly to UV-curable compounds comprising urethane and acrylate moieties which are especially useful as film formers, in particular for use in packaging and printing fields.
  • VOC's toxic volatile organic compounds
  • UV-curable coating systems generally utilise an oligomer starting material in combination with a reactive solvent (diluent) and a photoinitiator.
  • the photoinitiator is decomposed by exposure to the UV radiation, yielding free radicals or cations that initiate the polymerisation of the oligomer. Because the reactive diluent itself takes part in the overall polymerisation process, it does not evaporate, and therefore the resulting films are conventionally considered VOC-free.
  • UV- curable systems are not currently commercially used for the production of packaging or printable material for foodstuffs and other materials where health and safety concerns are important.
  • hyperbranched polyesters in the manufacture of UV- curable coatings is well known, for example from EP-A-1227076, EP-A-1070748, US-A- 6114489 and US-A-6093777.
  • hyperbranched polymers are highly branched with a large number of end groups, which can be exploited to determine the physical and chemical properties of the resulting polymer. For example, their melt- and solution-viscosities do not change considerably with any increase in molecular mass, which is of great importance in paints.
  • the typically large number of hydroxyl groups in such molecules offers significant possibilities for the tailoring of end properties of the resulting polymerised materials.
  • such hyperbranched polyester molecules typically include an acrylate moiety (so-called "urethane-acrylates”), which are again well documented in the literature, eg. WO-A- 1997/023520, WO-A- 1993/021259, US-A- 2002/0026015, in addition to the other references mentioned above).
  • urethane-acrylates an acrylate moiety
  • the above-discussed photoinitiator component still needs to be used, resulting in the same problems as discussed above.
  • the invention provides compounds of the following formula ay.
  • R is a residue of a hyperbranched polyester core moiety of the following general formula (II):
  • R is a core group which is a residue of a multifunctional aliphatic or aromatic polyol preferably having 2 or more, more preferably 3 or more, even more preferably 4, OH groups;
  • R is a residue of an aliphatic or aromatic carboxylic acid having one COOH group and two or more OH groups, wherein n is the hydroxy functionality of the said carboxylic acid and is 2 or more, and m is the functionality of the polyol core group R 1 and is at least 2;
  • R 3 is a residue of an isocyanate compound selected from any one of the following formulae (1) to (13): (1) (2)
  • R is a hydrogen atom or methyl group; x is 1 -10, preferably 1-8, more preferably 4-8;
  • R 5 is an alkylene group
  • R 6 is -OR 7 , -NR 7 R 8 , -SR 7 or R 9 , where R 7 and R 8 are the same or different and each is independently selected from: (i) an alkyl, acyl, aryl, alkene or alkyne group, (ii) a saturated or unsaturated, optionally aromatic, carbocyclic or heterocyclic group; wherein any of the above groups (i) and (ii) may be optionally substituted; and R 9 is selected from any of: H, an alkyl, aryl, alkene or alkyne group, a saturated or unsaturated optionally substituted carbocyclic or heterocyclic group, an alkylthio, alkoxycarbonyl, aryloxycarbonyl, carboxy, acyloxy, carbamoyl, cyano, dialkylphosphonato, diarylphosphonato, dialkylphosphinato or diarylphosphinato group; a (being the number of urethane-
  • step (2) Reacting the hyperbranched polyester compound from step (1) with a monohalogen carboxylic acid in an amount and under temperature conditions sufficient to react with a significant proportion, preferably from about 25 to about 50 %, of the OH groups therein;
  • R 6 is as defined above and M is a metal cation, preferably an alkali metal cation, in an amount corresponding to at least one mole of the compound (III) per halogen atom.
  • the invention further provides a method of preparing an ink, paint, coating or packaging film, comprising polymerising and/or crosslinking and/or curing a composition consisting of or containing at least one compound according to the first aspect of the invention, or at least one compound prepared by the method according to the second aspect of the invention, by irradiation with UV radiation, especially of from about 200 - 400 nm wavelength. Preferred embodiments of this aspect of the invention are described hereinbelow.
  • the present invention further provides a polymerisable composition comprising a compound according to the first aspect of the invention.
  • the present invention further provides an ink, paint, coating or packaging film per se, formed by the method according to the third aspect of the invention.
  • the multifunctional aliphatic or aromatic polyol is preferably an aliphatic or aromatic diol, triol, tetrol or alkoxylated monomer having 2 or more OH groups.
  • Examples of such preferred polyols include: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, pentanediol, neopentyl glycol, 1,3-propanediol, trimethylolpropane, trimethylolethane, glycerol, erythritol, ditrimethylolpropane, ditrimethylolethane, pentaerythritol, dipentaerythritol, tripentaerythritol, ethoxylated trimethylolethane, propoxylated trimethylolethane, ethoxylated trimethylolpropane, propoxylated trimethylolpropane, ethoxylated pentaerythritol and propoxylated pentaerythritol.
  • examples of the monofunctional carboxylic acid having two or more OH groups include: ⁇ , ⁇ -bis(hydroxymethyl)propionic acid (dimethylol propionic acid), ⁇ , -bis(hydroxymethyl)butyric acid, ⁇ , ⁇ - bis(hydroxymethyl)valeric acid, ⁇ , ⁇ -bis(hydroxyethyl)propionic acid, and ⁇ - phenylcarboxylic acids having at least two hydroxyl groups directly pendent to the phenyl ring (phenolic hydroxyl groups), such as 3,5-dihydroxybenzoic acid.
  • examples of the monohalogen carboxylic acid include: bromoacetic acid, 2-bromopropionic acid, 2-bromobutyric acid, 3-bromopropionic acid, 4-bromobutyric acid, 2-bromohexanoic acid, 2-bromo-3-methylbutyric acid, 2- bromophenylacetic acid, 2-bromotetradecanoic acid, 2-bromo-2-methylpropionic acid, and the same acids as just listed but with chloro and iodo monosubstituents instead of bromme.
  • the temperature conditions in this method step (2) are preferably a temperature of less than about 250°C, more preferably below about 210°C, even more preferably below about 160°C.
  • the compound (III) is preferably an alkali metal salt of alkyl xanthogenate.
  • a particularly preferred example is potassium alkyl xanthogenate.
  • This reaction step is preferably carried out in a solvent, such as ethylacetate, acetone, tetrahydrofuran, ethanol or methylethylketone, at ambient temperature for eg. 24 hours.
  • the obtained intermediate reaction mixture, containing salt from reaction may be used without further purification.
  • examples of the diisocyanate compound for preparing the adduct include: isophoronediisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, 4,4-diisocyanato-dicyclohexylmethane, toluene-2,4-diisocyante, toluene- 2,6-diisocyante, 1,4-diisocyanate cyclohexane, l,4-diisocyanato-4-methyl-pentane and l,3-bis(2-isocyanatoprop-2-yl)benzene).
  • hydroxyalkyl (meth)acrylate component examples include: 2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, polyethyleneglycol monoacrylate, polypropyleneglycol monoacrylate, polyethyleneglycol monomethacrylate, polypropyleneglycol monomethacrylate, 2- hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate).
  • the reaction of this method step is typically, and preferably, carried out in the presence of a catalyst, such as dibutyltindilaurate, at a temperature of below about 60°C, more preferably below about 40°C.
  • the reaction of the product of step (3) with the adduct of step (4) is preferably carried out in a solvent, such as ethylacetate, in the presence of an inhibitor for radical polymerisation, such as hydroquinone, and a suitable catalyst, such as dibutyltindilaurate.
  • a solvent such as ethylacetate
  • an inhibitor for radical polymerisation such as hydroquinone
  • a suitable catalyst such as dibutyltindilaurate.
  • the reaction is preferably carried out at a temperature of below about 100°C, more preferably below about 80°C.
  • the above purification step (6) preferably comprises filtering off the product, extracting the residual salt with water, drying the product with eg. anhydrous magnesium sulphate, filtering off the product again and evaporating the solvent.
  • additional components such as solvents, other polymerisable binders and conventional additives (eg. pigments, UV stabilisers, flow aids, etc) may be added to the product for preparing a practical UV-polymerisable composition for use in preparing useful polymerised end-products. Examples of this are given in the Examples hereinbelow.
  • the degree of modification of the OH end groups of the hyperbranched polyester can be important in determining the properties, especially the viscosity, of the ultimate UV-polymerised resins.
  • This degree of modification of the OH end groups of the hyperbranched polyester can be controlled by appropriate selection of the stoichiometric ratios between the hyperbranched polyester core compound starting material (from step 1), and/or the halogenated acid used in step (2), and or the urethane- acrylate adduct used in step (5) in the overall preparative process of the oligomers for polymerisation.
  • one mole of hyperbranched polyester second generation (see Example 1 hereinbelow) has 16 hydroxyl groups, and if 8 moles of urethane acrylic adduct is used, this results in -50% modification of the OH groups.
  • the degree of xanthate substitution in the subject oligomer compounds of the invention can be controlled by appropriate selection of the stoichiometric ratios between the OH groups of the hyperbranched polyester component and the halogenated carboxylic acid (introducing a halogen atom into the hyperbranched polymer in step (2)), since the halogen atom reacts quantitatively with the xanthate salt introduced in step (3). Again, examples of this are given in the Examples hereinbelow.
  • the choice of structure of the hydroxyalkyl (meth)acrylate component used in step (4) can also be important in determining the properties, especially the viscosity and reactivity, of the ultimate resins.
  • the use of long polyalkylene glycol monoacrylate chains to modify the hyperbranched polyester component lowers the viscosity of the resin by covering the highly polar groups (hydroxy or urethane) of the macromolecules, thereby reducing polar intermolecular interactions.
  • the use of Bisomer PEA6 (as in the Examples hereinbelow, which has flexible polyethyleneoxide chains) can give adducts of 558g/mol molecular weight, which considerably reduces the viscosity of the ultimate resin.
  • hydroxyethyl acrylate gives adducts of 338g/mol molecular weight, which is much more rigid and the ultimate resin obtained is of a significantly higher viscosity.
  • Polypropyleneglycol chains are bulkier and less polar than polyethyleneglycol chains, so they result in lower viscosity resins and the cured material is more resistant to polar solvents, particularly water.
  • Methacrylate resins have a lower reactivity and need more time for UV crosslinking. They also have an increased sensibility to oxygen inhibition. However, the obtained crosslinked materials feature higher hardness and mechanical strength. Acrylate resins are commonly used for UV curing because the reactivity of the system is the chief parameter (in most cases), which determines their final application.
  • the third aspect of the invention relates to the method of UV- polymerisation/crosslinking/curing of the subject novel compounds for preparing an ink, paint, coating or packaging film. This involves irradiation, under conventionally appropriate conditions, of a composition comprising at least one of the subject new oligomers with UV radiation, especially of from about 200 - 400 nm wavelength.
  • the UV-curable composition comprising it or them may further comprise one or more reactive diluents (preferably copolymerizable compounds having more than one double bond per molecule).
  • Examples of preferred reactive diluents include: hexanediol diacrylate, tripropylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipent
  • the amount of such reactive diluent(s) added to the reaction mixture is preferably such as to achieve a viscosity of the reactive composition which is from about 0.01 to about 50 Pas. This viscosity may be achieved by adding typically from about 90 to about 10 wt % of reactive diluent(s), as calculated on the weight of the total reaction mixture, preferably from about 30 to about 10 wt %.
  • the actual preferred amount of the reactive diluent(s) will depend on the desired viscosity, coat film thickness, method of application, field of application and the desired mechanical properties of the resulting polymerised material. Examples of this are given hereinbelow.
  • the reactive composition may in addition comprise conventionally appropriate amounts of any of the following optional adjunct components: solvents, pigments, matting agents, flow control agents, antioxidants, UV stabilisers, adhesion promoters, or other additives used in conventional UV-curing technology.
  • optional adjunct components solvents, pigments, matting agents, flow control agents, antioxidants, UV stabilisers, adhesion promoters, or other additives used in conventional UV-curing technology.
  • novel oligomers of the present invention be used as the sole UV- reactive constituent binder in UV-polymerisable/curable compositions according to the invention (which is preferred), but they may if desired be used in combination with a second binder based on a similarly structured hyperbranched urethane-acrylate oligomer but without the integral xanthate moiety but which can still be cured without the addition of a photoinitiator.
  • a second binder component may for example be a hyperbranched or conventional urethane acrylate or any binder containing unsaturated groups (eg. epoxy acrylate, polyester acrylate, polyether acrylate, unsaturated polyester, etc).
  • the new oligomers of the present invention may be used to prepare inks, paints, films and coatings for a variety of end uses. These include (but are not limited to): - printing inks for food packaging - UV-curable inks for ink-jet printers - flexographic inks - coatings for optical fibres, - scratch resistant coatings on computer discs, eg. CD's and DVD's, - dental composite resins, - stereolithography, automotive coatings, - wood coatings, - floor coatings, - adhesives.
  • HDDA Hexanediol diacrylate (ex BASF) Irgacure 184 1-hydroxy-cyclohexyl phenyl-ketone (ex Ciba Specialty Chemicals) Fascat 4100 Butylstannoic acid (ex Atofina)
  • Dendrimers are highly branched structures consisting of a central core from which treelike arms extend three-dimensionally into space, forming a more or less spherical or rod-shaped structure, depending on the type of core used. The number of branches increases systematically from the core of the molecule in a radial direction. Each successive layer of branches is called a generation. Dendrimers are synthhesized with the accurate control of each step by protection/deprotection schemes, to give perfectly branched monodispersed molecules. This is illustrated by the following scheme:
  • Hyperbranched macromolecules are made in a one-pot synthesis and this simplified procedure yields less perfect structures. The fact that they are produced using such simple procedures makes them more cost effective, and therefore more suitable for most commercial applications. Hyperbranched polymers have lower branching efficiency than dendrimers, but possess many of the same properties. The highly branched architecture minimizes chain-chain entanglements and so imparts both high solubility and low melt viscosity to these polymers. Hyperbranched polymers are not monodispersed like dendrimers (all molecules are not the same in size) but their molecular weight distribution is between dendrimer and classical linear polymers.
  • DITMP ditrimethylolpropane
  • the product had the following structure:
  • the product had the following structure:
  • the product had the following structure:
  • the product had the following structure:
  • the product had the following structure:
  • the product had the following structure:
  • Example 6 The procedure as specified in Example 6 was repeated with different amounts of hydroxy-acrylate monomers.
  • the theoretical composition of the hyperbranched urethane-acrylates of the obtained products is given in Table 1 below. Table 1
  • EXAMPLE 10 Synthesis of H2(X) 4 (PEA6) ⁇ 0 10.00 g of the product from Example 4 was dissolved in 25 ml of ethyl acetate in a 250 ml 3-necked flask. 2.93 g (0.018 mole) of KCS 2 OC 2 H 5 was dissolved in 10 ml of ethyl acetate. While stirring, the solution was added in small portions into the flask. The reaction mixture was stirred at room temperature overnight.
  • the product had the following structure:
  • Example 10 The procedure as specified in Example 10 was repeated with different amounts of isophorone diisocyanate and hydroxy acrylate monomers.
  • the theoretical composition of hyperbranched urethane-acrylates of the obtained products is given in Table 2 below. Table 2
  • Coating formulations comprising the products obtained in Examples 2 and 6 - 13 were prepared by adding 20 wt% of reactive diluent (HDDA). 4% of Irgacure 184 was added to the coating formulation comprising the oligomer obtained in Example 2.
  • the lacquers obtained were coated on steel panels at a film thickness of 60 ⁇ m.
  • the films were cured using a medium pressure halogen UV lamp - 80 W/cm (UVPS) by passing 10 times at a belt speed of 10 rn/min in nitrogen atmosphere. The films were allowed to stand overnight before testing.
  • the properties of the film obtained are given in Table 3 below.
  • Example 2 The product prepared in Example 2 was mixed with products obtained in Examples 5, 6 and 10 without the addition of photoinitiators. All the compositions contained 20 wt.% of the reactive diluent (HDDA). The compositions of these coating formulations are given in Table 4 below.
  • Living free radical polymerisation is a recently developed technique for controlled polymerisation of vinyl monomers. This technique allows the synthesis of a wide range of different materials (block, star, dendritic polymers, etc), which are not attainable via other polymerisation processes or are difficult to prepare.
  • the living character is used for the generation of a new portion of free radicals upon irradiation with UV light.
  • the controllable character of this reaction is due to the reversibility of the breaking the C-S bond under UV light. This process is explained by the following mechanism:
  • the C-S bond undergoes photolysis giving the macroradical (I), on the one hand, and the dormant radical (II), on the other.
  • the dormant radical cannot initiate the reaction of polymerisation; only the macroradical (I) reacts with monomer (III) (reactive diluent), causing chain growth (crosslinking, in the case of preferred embodiments of the present invention).
  • the macroradical (I) is exclusively attached to the oligomer, which means that there is no possibility of creating any other polymer chain which is not connected to the oligomer (ie. there is low content of extractable material).
  • the dormant radical can react with the growing macroradical, causing its deactivation.
  • the obtained material has terminal xanthate groups which may again undergo photolysis under UV light. Since it is a crosslinking reaction, it is not a controlled polymerisation, but the mechanism possesses a living character - the reaction continues upon new UV irradiation until all molecules of the monomers are consumed. That means that by curing, the present invention is able to make an active surface coating with xanthate groups embedded therein. This property can be exploited for various purposes, as already described herein (eg. grafting, sensoring, printing, etc.).
  • Urethane-acrylates are the most important binder for coating optical fibres.
  • the chief requirements for a binder in this field are very fast curing (ie. very reactive resins) and good mechanical properties for protection and reinforcement of the glass fibre.
  • the primary coatmg layer is soft (made of flexible resin with a low Tg and modulus) and applied directly onto the glass fibre, while the secondary coating layer (made of hard resin with a higher Tg and modulus) is coated over the primary layer to protect the fibre during handling.
  • the resins produced according to the present invention are very easy to adjust to fulfil these requirements (the degree and type of modification of the hyperbranched core) and to make them ideal candidates for such applications.
  • Typical UV-curable optical fibre coating compositions of the present invention may comprise from about 20 to about 90 % by weight, preferably from about 50 to about 75 % by weight, of urethane-acrylate oligomer(s) of the present invention, from about 10 to about 90 % by weight, preferably from about 25 to about 40 % by weight of reactive diluent(s), and from 0 to about 10 % by weight, preferably from about 1 to about 5 % by weight of additive(s) (adhesion promoters, stabilisers, etc).
  • additive(s) adheresion promoters, stabilisers, etc.
  • UV-curable ink jet printing is a new area of digital imaging.
  • the main requirements for UV-curable materials in this technology are fast curing, low viscosity, good droplet formation and good cured film properties (such as scratch resistance, adhesion, hardness, flexibility, sharpness of image).
  • the main advantages of UV-curing inks and coatings in this field are: - they emit little or no VOC solvents, - they will not dry during the printing process, but will dry almost instantly when cured ("drop on demand"), - they permit high production rates, - they produce the highest printed gloss available and high quality matt and satin finishes, - they produce chemically durable and abrasion resistant prints, - the curing equipment occupies much less space than conventional thermal drying equipment.
  • the resins produced according to the present invention can be designed to have a high concentration of unsaturated groups yielding attractive physical properties of the cured films. At the same time, they can have very low shrinkage upon curing (which is a big problem in conventional UV coatings, not just in ink jet printing), owing to their very high molecular weight, giving good adhesion to different substrates.
  • Typical UV-curable ink jet coating compositions according to the present invention may comprise from about 10 to about 60 % by weight, preferably from about 20 to about 40 % by weight of the urethane-acrylate oligomer(s) of the invention, from about 10 to about 80 % by weight, preferably from about 40 to about 60 % by weight, of reactive diluent(s) (preferably alkoxylated di- or tri- functional monomers), from 0 to about 30% by weight, preferably from about 5 to about 15 % by weight of pigment(s), and from 0 to about 20 % by weight, preferably from about 5 to about 10 % by weight of additive(s).
  • Another application of the resins produced accordmg to the present invention is their use for flexographic inks.
  • the rheology of UV flexographic inks is quite different from other types of inks.
  • Resins for flexographic inks must behave like Newtonian liquids (viscosity remains constant at any shear rate or shear stress).
  • the resins produced according to the present invention can exhibit such Newtonian behaviour (because hyperbranched or star structures minimize chain-chain entanglements, which is responsible for pseudo-plastic behaviour), and are therefore ideal candidates for this application.
  • Resins produced according to the present invention can have a polar shell (arms of polyethylene glycol) and a less polar core (hyperbranched polyester), which makes them good agents for the dispersions of pigments.
  • Typical UV-curable flexographic ink compositions accordmg to the present invention may comprise from about 10 to about 40 % by weight, preferably from about 15 to about 25 % by weight, of urethane acrylate oligomer(s) of the invention, from about 10 to about 90 % by weight, preferably from about 40 to about 60 % by weight of reactive diluent(s), from 0 to about 30% by weight, preferably from about 10 to about 20 % by weight, of pigment(s), and from 0 to 20 % by weight, preferably 5 to 10 % by weight of additive(s).
  • the UV-curable oligomers of the present invention may also be used for automotive coatings as an alternative to the conventional two-pack polyurethane/acrylate clearcoats. Furthermore, they can be used as a component of a dual curing coating composition based on polyurethane/acrylate coatings, giving better scratch and abrasion resistance of clearcoats.
  • the resins of this invention comprise some free hydroxyl groups, so they can react with the second component from the two-pack system (ie. the polyisocyanate component). As a result, the obtained films (crosslinked coatings) have a good balance of hardness and flexibility.
  • known UV-curable compositions are generally considered to be VOC-free.
  • solvents examples include: ketones, ethers and esters, such as ethyl acetate, n-butyl acetate, methyl ethyl ketone, N-methylpyrrolidone, tetrahydro furan, l-methoxy-2-propanol, methoxy propyl acetate.
  • binders eg. conventional acrylic polyols based on hydroxyacrylates and methacrylates, as are well known in the art, eg. Desmophen A365, ex Bayer AG
  • crossslinkers eg. conventional acrylic polyols based on hydroxyacrylates and methacrylates, as are well known in the art, eg. Desmophen A365, ex Bayer AG.
  • Typical such dual-curing formulations containing urethane-acrylate resins of the present invention may comprise from about 10 to about 60 % by weight, preferably from about 20 to about 40 % by weight, of the urethane-acrylate oligomer(s) of the invention, from about 10 to about 60 % by weight, preferably from about 20 to about 40 % by weight of conventional acrylic polyol, from about 10 to about 40 % by weight, preferably from about 20 to about 40 % by weight, of reactive diluent(s), from about 5 to about 30 % by weight, preferably from about 10 to about 20 % by weight, of a crosslinker, and from 0 to about 10 % by weight, preferably from about 1 to about 5 % by weight, of additive(s).
  • This Example demonstrates the advantageous property of compounds according to the invention in terms of their greatly reduced (or even eliminated) degree of inhibition by oxygen when UV-crosslinked under an air atmosphere.
  • Coating formulations comprising the products obtained in each of Comparative Example 15 and Examples 2, 6, 7, 12 and 13 were prepared by adding thereto 20 wt % of reactive diluent (HDDA). 4 wt % of photoinitiator (Irgacure 184) was added to the coating formulations comprising the oligomers obtained in Comparative Example 15 and Example 2.
  • the coating formulations were then coated onto steel plates and cured using a medium pressure halogen UV lamp (80 W/cm) by passing each one 10 times thereunder at a belt speed of 10 m min in an air atmosphere.
  • the resulting properties of the obtained films are given in Table 7 below.
  • Finger touch test - tacking + tack-free (no air inhibition)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne de nouveaux composés polymérisables par ultraviolets de la formule suivante (I) où R représente un résidu d'une fraction principale de polyester hyperramifiée de la formule générale (II) suivante où Rl représente un groupe principal qui est un résidu d'un polyol aliphatique ou aromatique multifonctionnel; R2 représente un résidu d'un acide carboxylique aromatique ou aliphatique ayant un groupe COOH et au moins deux groupes OH, n représentant la fonctionnalité hydroxy de cet acide carboxylique et valant 2 minium, et m représentant la fonctionnalité du groupe principal de polyol Rl et valant 2 minimum; R3 représente un résidu d'un composé diisocyanate ; R4 représente un atome hydrogène ou un groupe méthyle; x vaut 1 à 10, de préférence 4 à 8; R5 représente un groupe alkylène; R6 représente -OR7, -NR7R8, -SR7 ou R9, R7 et R8 étant identiques ou différents et étant respectivement et indépendamment sélectionnés parmi: (v) un groupe alkyle, acyle, aryle, alcène ou alkyne, (vi) un groupe carbocyclique ou hétérocyclique, éventuellement aromatique, saturé ou non saturé; l'un quelconque des groupes susmentionnés (i) et (ii) pouvant être éventuellement substitué; et R9 est sélectionné parmi H, un groupe alkyle, aryle, alcène ou alkyne, un groupe carbocyclique ou hétérocyclique éventuellement substitué, saturé ou non saturé, un groupe alkylthio, alcoxycarbonyle, aryloxycarbonyle, carboxy, acyloxy, carbamoyl, cyano, dialkylphosphonate, diarylphosphonate; dialkylphosphinate ou diarylphosphinate; a (représentant le nombre de chaînes d'acrylate d'uréthane attachées au groupe principal central R) vaut 0 à 10, de préférence 1 à 10, idéalement 4 à 10; b (représentant le nombre de fractions de xanthate dans la molécule) vaut 0 à 10, de préférence 1 à 10, idéalement 4 à 10 sous réserve que a + b fasse 2 à 16, de préférence 10 à 14. La polymérisation par ultraviolets des nouveaux composés qui comportent à la fois des fractions d'acrylate d'uréthane et de xanthate, permet d'éviter les problèmes de photo-initiateur résiduel ou de monomère n'ayant pas réagi dans les produits polymérisés finaux. En tant que tels, ils sont principalement utiles dans la production d'encres d'impression et de films d'emballage destinés à des denrées alimentaires ainsi que comme divers revêtements.
PCT/GB2003/003239 2003-07-16 2003-07-16 Composes d'acrylate d'urethane a durcissement induit par la lumiere WO2005014679A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2003251350A AU2003251350A1 (en) 2003-07-16 2003-07-16 Photo-curable urethane-acrylate compounds
PCT/GB2003/003239 WO2005014679A1 (fr) 2003-07-16 2003-07-16 Composes d'acrylate d'urethane a durcissement induit par la lumiere

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/GB2003/003239 WO2005014679A1 (fr) 2003-07-16 2003-07-16 Composes d'acrylate d'urethane a durcissement induit par la lumiere

Publications (1)

Publication Number Publication Date
WO2005014679A1 true WO2005014679A1 (fr) 2005-02-17

Family

ID=34130881

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2003/003239 WO2005014679A1 (fr) 2003-07-16 2003-07-16 Composes d'acrylate d'urethane a durcissement induit par la lumiere

Country Status (2)

Country Link
AU (1) AU2003251350A1 (fr)
WO (1) WO2005014679A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1714633A1 (fr) * 2005-04-20 2006-10-25 Heraeus Kulzer GmbH Matériaux dentaires contenant les composés dendritiques
WO2010108863A1 (fr) * 2009-03-24 2010-09-30 Basf Se (meth)acrylates de polyuréthane à haute fonctionnalité durcissables par rayonnement
WO2014031084A1 (fr) * 2012-08-23 2014-02-27 Nipsea Technologies Pte Ltd Procédé de formation de compositions polymères à double durcissement
WO2016086631A1 (fr) * 2014-12-01 2016-06-09 合众（佛山）化工有限公司 Procédé de préparation d'une résine photodurcissable de polyester aqueux modifié par un isocyanate cycloaliphatique
CN114773538A (zh) * 2022-04-11 2022-07-22 山东微观生态研究中心有限公司 一种微交联星型絮凝剂、制备方法及其在污水处理中的应用
CN114835889A (zh) * 2022-05-13 2022-08-02 深圳市百利合新材料发展有限公司 超支化聚合物分子结构、制备方法以及基于超支化聚合物的光刻胶
CN116804130A (zh) * 2023-05-05 2023-09-26 无锡琳华新材料科技有限公司 一种低voc的tpo汽车内饰材料及其生产工艺

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6051733A (en) * 1996-02-22 2000-04-18 Ucb, S.A. Sulfur-containing compounds for optical grade polymeric casting compositions
WO2001083393A2 (fr) * 2000-05-01 2001-11-08 Dsm N.V. Composition de resine liquide durcissable pour fibres optiques

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6051733A (en) * 1996-02-22 2000-04-18 Ucb, S.A. Sulfur-containing compounds for optical grade polymeric casting compositions
WO2001083393A2 (fr) * 2000-05-01 2001-11-08 Dsm N.V. Composition de resine liquide durcissable pour fibres optiques

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1714633A1 (fr) * 2005-04-20 2006-10-25 Heraeus Kulzer GmbH Matériaux dentaires contenant les composés dendritiques
DE102005018451A1 (de) * 2005-04-20 2006-11-02 Heraeus Kulzer Gmbh Dentalmaterialen, enthaltend dendritische Verbindungen
DE102005018451B4 (de) * 2005-04-20 2008-07-24 Heraeus Kulzer Gmbh Verwendung von dendritischen Verbindungen in Dentalmaterialien
CN102361620B (zh) * 2009-03-24 2014-09-03 巴斯夫欧洲公司 辐射固化的高官能聚氨酯(甲基)丙烯酸酯
CN102361620A (zh) * 2009-03-24 2012-02-22 巴斯夫欧洲公司 辐射固化的高官能聚氨酯(甲基)丙烯酸酯
WO2010108863A1 (fr) * 2009-03-24 2010-09-30 Basf Se (meth)acrylates de polyuréthane à haute fonctionnalité durcissables par rayonnement
US9200108B2 (en) 2009-03-24 2015-12-01 Basf Se Radiation-curing, highly functional polyurethane (meth)acrylate
WO2014031084A1 (fr) * 2012-08-23 2014-02-27 Nipsea Technologies Pte Ltd Procédé de formation de compositions polymères à double durcissement
WO2016086631A1 (fr) * 2014-12-01 2016-06-09 合众（佛山）化工有限公司 Procédé de préparation d'une résine photodurcissable de polyester aqueux modifié par un isocyanate cycloaliphatique
CN114773538A (zh) * 2022-04-11 2022-07-22 山东微观生态研究中心有限公司 一种微交联星型絮凝剂、制备方法及其在污水处理中的应用
CN114835889A (zh) * 2022-05-13 2022-08-02 深圳市百利合新材料发展有限公司 超支化聚合物分子结构、制备方法以及基于超支化聚合物的光刻胶
CN116804130A (zh) * 2023-05-05 2023-09-26 无锡琳华新材料科技有限公司 一种低voc的tpo汽车内饰材料及其生产工艺
CN116804130B (zh) * 2023-05-05 2024-04-09 无锡琳华新材料科技有限公司 一种低voc的tpo汽车内饰材料及其生产工艺

Also Published As

Publication number Publication date
AU2003251350A1 (en) 2005-02-25

Similar Documents

Publication Publication Date Title
KR100897985B1 (ko) 다양하게 옥스알킬화된 폴리올의 혼합물을 기재로 하는,방사선-경화성 우레탄 아크릴레이트
JP6240151B2 (ja) 放射線硬化性（メタ）アクリル化化合物
US8048979B2 (en) Process for synthesis of telechelic urethane acrylate UV curable pre-polymeric materials
JP2003510432A (ja) Ｕｖ線で硬化可能および熱的に硬化可能な水性ポリウレタン分散液ならびに該分散液の使用
TW201345948A (zh) 輻射可硬化（甲基）丙烯酸化化合物
EP2271688B1 (fr) Acrylate de polyuréthane modifié
TWI634132B (zh) 輻射可固化之化合物
CN110352204A (zh) 水性涂料组合物
KR20190039746A (ko) 시클릭 구조 요소, 우레탄 / 우레이도 연결 및 자유 라디칼-중합성 작용기를 함유하는 화합물
EP2065412A1 (fr) Composés d'addition de polyisocyanates éthyléniquement unsaturés à base de triisocyanate de lysine, leur utilisation dans les compositions de revêtement et leur procédé de préparation
WO2005014679A1 (fr) Composes d'acrylate d'urethane a durcissement induit par la lumiere
JP4678466B2 (ja) エネルギー線硬化型樹脂組成物
JP2017048301A (ja) ウレタン（メタ）アクリレート、活性エネルギー線硬化性組成物、及びその硬化物
WO2016093005A1 (fr) (méth)acrylate d'uréthane, composition de (méth)acrylate d'uréthane durcissable par un rayonnement d'énergie active et article durci associé
EP1347003A1 (fr) Composition de résine durcissable sous irradiation
JPS59191772A (ja) 被覆，接着用組成物
KR20160011637A (ko) 우레탄（메트）아크릴레이트의 제조 방법
CN113853412A (zh) 具有户外性能的可固化的组合物
JP3377084B2 (ja) 活性エネルギー線硬化性樹脂組成物
CN113817086B (zh) 一种生物基光固化树脂组合物及其制备方法和应用
CN112851596B (zh) 一种含恶唑烷可辐射固化的氨酯（甲基）丙烯酸酯及其制备方法
SE540989C2 (en) Novel oligomer or polymer and composition comprising the same
JPS5974116A (ja) ラジカル重合性プレポリマ−の製法
Şabani Synthesis and characterization of hyperbranched polyester based polymers and their application on uv-curable wood coatings
JP2004307783A (ja) 活性エネルギー線硬化性樹脂組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: JP