TREA

Reactive diluents and alkyd resin coating compositions

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Information

  • Patent Application
  • 20050096406
  • Publication Number
    20050096406
  • Date Filed
    February 25, 2003
    21 years ago
  • Date Published
    May 05, 2005
    19 years ago
Information
Abstract
The invention relates to new reactive diluents of the formulae (Ia, Ib, Ic, Id, Ie) and to an alkyd coating composition comprising them. In a preferred embodiment R1 and R2 are hydrogen; R3 is (meth)acryloyloxy-methyl or phenyl para substituted by vinyl, R4 is phenyl or phenyl para substituted by vinyl or (meth)acryloyloxy; or a substituted phenyl residue of the formula —C6H4CH2—W, wherein W is (meth)acryloyloxy, or an aliphatic residue of the formula —CH2—Y-A, wherein Y is a bond, O—C1-C12alkylene, wherein the alkylene linker is linear or branched and may be interrupted once or more than once by oxygen, A is hydroxy, C1-C6alkoxy, acetoxy, (meth)acryloyloxy, or a phthalate- or maleate-residue; R5 is hydrogen; n is 1; X is —(CH2)—. The invention further relates to a solvent-based or water-based alkyd coating composition comprising 0.3 to 10 wt. % of a mono-, bis- or trisacylphosphinoxide photoinitiator, especially Irgacure 819.
Description

The invention relates to new reactive diluents and to a coating composition based on an alkyd resin containing them.


Alkyd resins are commonly used for solvent-based or water based coating systems. Alkyd resins are formed through the incorporation of unsaturated fatty acid esters into polyester or polyurethane chain-extended polymer systems. Curing is obtained via auto-oxidative crosslinking.


Conventional alkyd resin systems contain a solvent, an anti skinning agent and a siccative. The solvent will usually be an organic solvent.


Examples of antiskinning agents may be classified as antioxidants, blocking agents, solvents or retention agents. The European Patent Publication EP 1 103 583A1 describes aldoximes or ketoximes as antiskinning agents.


The cure-process involves oxidation, i.e. reaction with oxygen from the air. It is always performed in the presence of a catalyst, usually called a “drier” or “siccative”, which is usually a combination of metal salts. Those catalysts are well-known in the art and commercially available. Examples of suitable driers are metal salts of (cyclo)aliphatic, natural or synthetic acids, such as, for example, linoleic acid, naphthenic acid and 2-ethyl-hexanoic acid. Cobalt, manganese, lead, zirconium, calcium and zinc are suitable metals. Mixtures of driers can, of course, also be used. In terms of their metal content, the driers are used in a proportion of 0.001 to about 3% by weight, relative to the binder solids content.


It has been suggested to replace the solvent by reactive diluents which are usually compounds or mixtures of compounds of relatively low viscosity, a relatively high boiling point (i.e. low saturated vapor pressure) which act as solvents during the formulation and processing of the coating. Such reactive diluents can copolymerize with a resin thereby reducing losses of the solvent to atmosphere on drying of the coating.


WO 9702230 describes the use of 2-(2,7-octadienoxy) di(2,7-octadienyl) succinate as a reactive diluent in a paint or coating formulation.


WO 9800387 describes the use of a composition comprising a mixture of a fumarate, maleate and 2-allyloxy-succinate esters as a reactive diluent in a paint or coating formulation.


EP 072 127 describes an alkyd resin system containing a reactive diluent selected from the group consisting of dicyclopentenyl methacrylate and dicyclopentenyloxyalkyl methacrylate.


Japanese Patent Application JP2001226466A2 describes the polymerization of norbornene in the presence of allyl methacrylate and bis(tricyclohexylphosphine)benzylidene ruthenium dichloride to give methacryloyl-terminated polymers. Low viscous compounds are not described.


There is still a need to provide cobalt-free alkyd resin systems having a markedly reduced solvent content or being solvent free and showing a similar drying performance.


It has now been found that the compounds of formula Ia-Ie as defined below can be used as reactive diluents thus, replacing the solvent completely or partially.


The invention relates to compounds of the formula Ia-Ie
embedded image

wherein

  • R1 and R2 independently of one another are hydrogen, hydroxy, cyano, halogen, vinyl, formyl, a residue of acrylic acid, C1-C6alkoxycarbonyl, C1-C6alkylaminocarbonyl, phenylcarbonyl, C1-C6alkylcarbonyloxy, C1-C6alkenylcarbonyloxy, (meth)acryloyloxy, (meth)acryloyl-C1-C6alkylamino, di[(meth)acryloylC1-C6alkyl]amino, unsubstituted C1-C12alkyl or C1-C12alkyl substituted by hydroxy, halogen, ethynyl, C1-C6alkylamino, di(C1-C6)alkylamino, (meth)acryloyloxy, (meth)acryloylC1-C6alkylamino, di[(meth)-acryloylC1-C6alkyl]-amino or by tolylaminocarbonyloxy;
  • R3 is (meth)acryloyloxy-C1-C6alkyl or phenyl substituted once or more than once by hydroxy, halogen, cyano, vinyl, C1-C12alkyl, C1-C6alkoxy, phenoxy, benzyloxy, acetoxy, C1-C6alkoxycarbonyloxy, C1C6alkylcarbonyloxy, trifluormethyl, (meth)acryloyloxy, (meth)acryloylC1-C6alkylamino, di[(meth)acryloylC1-C6alkyl]amino; or R3 is 1-naphthyl, 2-naphthyl, biphenyl, anthracenyl; or R3 is a substituted phenyl residue of the formula —C6H4—CH2—W, wherein
    • W signifies hydroxy, halogen, cyano, acetoxy, acetylsulfanyl, trifluormethylcarbonyloxy, (meth)acryloyloxy, (meth)acryloylC1-C6alkylamino, di[(meth)acryloylC1-C6alkyl]amino, C1-C12alkoxy, C1-C12alkoxy substituted once or more than once by fluor, C1-C12alkoxy substituted by epoxyethyl; or W is dimethylamino, dimethylammonium, or W is a residue selected from an amino butyric acid or from an an ε-caprolactame, or W is sulfonato, C1-C6alkylsulfonyl or C1-C6alkylsulfanyl, wherein the alkyl group is unsubstituted or substituted by chlorine; or W is a silanol residue or a residue of a phosphonic acid;
  • R4 is hydrogen, phenyl, 1-naphthyl, 2-naphthyl, biphenyl, anthracenyl, phenyl substituted once or more than once by hydroxy, halogen, cyano, vinyl, C1-C12alkyl, C1-C6alkoxy, phenoxy, benzyloxy, acetoxy, C1C6alkoxycarbonyloxy, C1-C6alkylcarbonyloxy, trifluormethyl, (meth)acryloyloxy, (meth)acryloylC1-C6alkylamino, di[(meth)acryloylC1-C6alkyl]amino, or R4 is a substituted phenyl residue of the formula —C6H4—CH2—W, wherein
    • W signifies hydroxy, halogen, cyano, acetoxy, acetylsulfanyl, trifluormethylcarbonyloxy, (meth)acryloyloxy, (meth)acryloylC1-C6alkylamino, di[(meth)acryloylC1-C6alkyl]amino, C1-C12alkoxy, C1-C12alkoxy substituted once or more than once by fluor, C1-C12alkoxy substituted by epoxyethyl; or W is dimethylamino, dimethylammonium, or W is a residue selected from an amino butyric acid or from an an ε-caprolactame, or W is sulfonato, C1-C6alkylsulfonyl or C1-C6alkylsulfanyl, wherein the alkyl group is unsubstituted or substituted by chlorine; or W is a silanol residue or a residue of a phosphonic acid; or
  • R4 is an aliphatic residue of the formula —(CR6R7)mY-A, wherein
    • R6 and R7 independently of one another are hydrogen, C1-C12alkyl or phenyl;
    • m is 1-10,
    • Y is a bond, O—C1-C12alkylene, wherein the alkylene linker is linear or branched and may be interrupted once or more than once by oxygen,
    • A is hydroxy, C1-C6alkoxy, phenoxy, phenylcarbonyloxy, formyloxy, acetoxy, benzoyloxy, (meth)acryloyloxy, (meth)acryloyl-C1-C6alkylamino, di[(meth)acryloylC1-C6alkyl]amino; or a phthalate or maleate-residue; or
  • R4 is a residue of the formula A or B
    embedded image
  • R5 is hydrogen or C1-C6alkyl;
  • n is a number of 1-10;
  • X is —(CH2)1-4—, —CR8R9—, —CO—, —O—, —NR10, —S—,
    • R8 and R9 independently of one another are hydrogen, unsubstituted C1-C6-alkyl or C1-C6-alkoxy, C1-C6-alkyl substituted by OH, C1-C6-alkoxy or halogen; unsubstituted aryl or aryl substituted by C1-C4-alkyl, OH, C1-C6alkoxy or halogen; or C1-C6alkylcarbonyloxy or phenylcarbonyloxy,
    • R10 is hydrogen, unsubstituted C1-C6-alkyl or C1-C6-alkyl substituted by OH— or C1-C4alkoxy;
    •  unsubstituted phenyl or phenyl substituted by OH—, C1-C4alkyl- or C1-C4alkoxy.


Furthermore, the invention relates to a coating composition comprising

  • (1) an alkyd resins,
  • (2) a photoinitiator,
  • (3) a reactive diluent of formula Ia-Ie as described above or mixtures thereof, and
  • (4) optionally a solvent.


    Definitions:


    Alkyd Resin


Alkyd resins are well known in the art and are readily available commercially.


Examples of resins that may be present include alkyd resins, epoxy-esters, urethane-alkyds and further modified oils.


Air drying alkyd resins are esters from drying oils, such as linseed oil, soybean oil, tungoil and other oils having unsaturated groups in there alkyl chain.


The alkyd resins can be classified as “long oil” alkyd resins containing more than 60 wt % of oil portion “medium oil” alkyd resins containing from 40 to 60 wt % of oil portion and “short oil” alkyd resins containing less than 40 wt % of oil portion. The alkyd resins are described in Ullmann's Encyclopedia, 6th edition 1999.


Longoil alkyd resins are especially known as good dispersing resins for a wide variety of pigments.


The resin may be present in an amount of between 5 and 50 wt %, based on the weight of the liquid coating composition. In high solid systems the resin is present in an amount >50 wt %. The alkyd may also be a water dilutable alkyd resins obtained by mixing (unmodified) alkyd resins with emulsifiers or may be a self-emulsifying alkyd resins with an chemically incorporated emulsifier.


Solvent


Solvents used in alkyd resins are aliphatic, cycloaliphatic and aromatic hydrocarbons such as mineral spirits known as white spirit, as well as xylene, toluene, alcohol ethers, glycol ethers, ketones, esters, alcohol ether acetates or mixtures thereof. As mentioned above, the solvent is not necessary to perform the inventive coating.


Photoinitiator


Any photoinitiator known to be useful for curing ethylenically unsaturated polymerizable compounds with daylight or with light sources equivalent to daylight or with UV-light may be used. The radiation employed is guided essentially by the absorption of the photoinitiators used. Suitable radiation sources are known. They can, for example, comprise lamps or lasers. Suitable UV lamps are mercury vapor lamps or UV lasers. The period of irradiation depends on the nature of the light source; It can range from seconds to minutes. Preference is given to the use of daylight.


Suitable photoinitiators are selected from benzophenones, benzophenone derivates such as, for example, halomethyl benzophenones, acetophenones, acetophenone derivates such as, for example, dialkoxyacetophenones, halomethylacetophenones, α-hydroxy or α-amino-acetophenones (1-benzoyl-1-hydroxy-1-methylethane or (4-morpholino-benzoyl)-2-benzoyl-2-dimethylamino-propane or (4-methylthio-benzoyl)-1-methyl-1-morpholinoethane), α-sulfonyl acetophenones; halomethylarylsulfones, 4-aroyl-1,3-dioxolanes, anthracene derivatives, thioxanthone derivatives, 3-ketocumarine derivatves, anthraquinone derivatives, benzoin alkylethers and benzil ketals, phenylglyoxalates and derivates thereof, dimeric phenylglyoxalates, peresters, monoacylphosphinoxides, bisacylphosphinoxides, trisacylphosphinoxides, halomethyltriazines, titanocenes, borates, O-acyloximes or camphor quinones. The photoinitiators may be used alone or in combination with suitable co-initiators.


Especially suitable are coating compositions comprising 0.3 to 10 wt. % of a mono-, bis- or trisacylphosphinoxide photoinitiator of the formula I
embedded image

wherein

  • X is O or S;
  • R1 and R2 independently of one another are linear or branched C1-C12-alkyl, C1-C12-alkoxy, phenyl, unsubstituted or optionally substituted by OR8, SR9, NR10R11, C1-C12-Alkyl or halogen; or
  • R1 and R2 are phenyl-C1-C4-alkyl or
    embedded image
    • R3 and R7 independently of one another are C1-C12-alkyl, C1-C12-alkoxy or halogen;
  • R4, R5 and R6 independently of one another are hydrogen, C1-C12-alkyl, C1-C12-alkoxy or halogen;
  • R8, R9 R10 and R11 independently of one another are hydrogen, C1-C12-alkyl, C2C12-alkenyl, benzyl or C2C20-alkyl interrupted once or several times by —O; or R10 and R11 represent together with the N-atom that they are attached to an optionally oxygen- or —NR12-containing 5 or 6 membered ring;
  • R12 is hydrogen, phenyl-C1-C4-alkyl or C1-C12-alkyl.


Preferred are compounds of the formula I′
embedded image

wherein

  • R1 and R2 independently of one another are C1-C8-alkyl, C1C6-alkoxy, phenyl that is unsubstituted or optionally substituted by one or two OR8 or NR10R11; or
  • R1 is
    embedded image
  •  and R2 is C1-C12-alkyl or phenyl unsubstituted or optionally substituted by OR8;
  • R3 and R7 independently of one another are C1-C4-alkyl, C1-C4-alkoxy, or chlorine;
  • R4, R5 and R6 independently of one another are hydrogen or C1-C4-alkyl,
  • R8 is C1-C8alkyl;
  • R10 and R11 represent together with the N-atom that they are attached to an optionally oxygen-containing 5 or 6 membered ring.


Especially preferred are compounds of the formula I′, in which
embedded image

wherein

  • R1 and R2 independently of one another are C1-C2-alkoxy or phenyl; or
  • R1 is
    embedded image
  •  and R2 is C1-C8-alkyl or phenyl that is unsubstituted or optionally substituted by one or two OR8;
  • R3 and R7 independently of one another are methyl, methoxy, or chlorine;
  • R5 is hydrogen or methyl;
  • R4 and R6 are hydrogen,
  • R8 is C1-C6-alkyl;


Most preferred is bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.


Bisaxcylphosphine oxides are described in EP-B-184095 or U.S. Pat. No. 4,737,593.


Illustrative examples of photoinitiators described in U.S. Pat. No. 5,534,559 and useful in the daylight curable compositions are:

  • bis(2,4,6-trimethylbenzoyl)methylphosphine oxide
  • bis(2,4,6-trimethylbenzoyl)ethylphosphine oxide
  • bis(2,4,6-trimethylbenzoyl)-isopropylphosphine oxide
  • bis(2,4,6-trimethylbenzoyl)-n-propylphosphine oxide
  • bis(2,4,6-trimethylbenzoyl)-n-butylphosphine oxide
  • bis(2,4,6-trimethylbenzoyl)-tert-butylphosphine oxide
  • bis(2,4,6-trimethylbenzoyl)-(2-methyl-prop-1-yl)phosphine oxide
  • bis(2,4,6-trimethylbenzoyl)-(1-methyl-prop-1-yl)phosphine oxide
  • bis(2,4,6-trimethylbenzoyl)-cyclohexylphosphine oxide
  • bis(2,4,6-trimethylbenzoyl)-n-pentylphosphine oxide
  • bis(2,4,6-trimethylbenzoyl)-n-hexylphosphine oxide
  • bis(2,4,6-trimethylbenzoyl)-(2-ethyl-hex-1-yl)phosphine oxide
  • bis(2,4,6-trimethylbenzoyl)-n-octylphosphine oxide
  • bis(2,4,6-trimethylbenzoyl)-(2,4,4-trimethyl-pent-1-yl)phosphine oxide
  • bis(2,4,6-trimethylbenzoyl)-n-decylphosphine oxide
  • bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819)
  • bis(2,4,6-trimethylbenzoyl)-(4-methylphenyl)phosphine oxide
  • bis(2,6-dimethylbenzoyl)-methylphosphine oxide
  • bis(2,6-dimethylbenzoyl)-ethylphosphine oxide
  • bis(2,6-dimethylbenzoyl)-i-propylphosphine oxide
  • bis(2,6-dimethylbenzoyl)-n-propylphosphine oxide
  • bis(2,6-dimethylbenzoyl)-(2,4,4-trimethyl-pent-1-yl)phosphine oxide
  • bis(2,6-dimethylbenzoyl)-(2-methyl-prop-1-yl)phosphine oxide
  • bis(2,6-dimethylbenzoyl)-n-butylphosphine oxide
  • bis(2,6-dimethylbenzoyl)-t-butylphosphine oxide
  • bis(2,6-dimethylbenzoyl)-(1-methyl-prop-1-yl)phosphine oxide
  • bis(2,6-dimethylbenzoyl)-cyclohexylphosphine oxide
  • bis(2,6-dimethylbenzoyl)-n-pentylphosphine oxide
  • bis(2,6-dimethylbenzoyl)-n-hexylphosphine oxide
  • bis(2,6-dimethylbenzoyl)-(2-ethyl-hex-1-yl)phosphine oxide
  • bis(2,6-dimethylbenzoyl)-n-octylphosphine oxide
  • bis(2,6-dimethylbenzoyl)-(2,4,4-trimethyl-pent-1-yl)phosphine oxide
  • bis(2,6-dimethylbenzoyl)-phenylphosphine oxide
  • bis(2,6-dimethylbenzoyl)-(2,5-dimethylphenyl)phosphine oxide
  • bis(2,6-dimethylbenzoyl)-n-octylphosphine oxide
  • bis(2,4,6-triethylbenzoyl)-methylphosphine oxide
  • bis(2,4,6-triethylbenzoyl)-ethylphosphine oxide
  • bis(2,4,6-triethylbenzoyl)-i-propylphosphine oxide
  • bis(2,4,6-triethylbenzoyl)-n-propylphosphine oxide
  • bis(2,4,6-triethylbenzoyl)-n-butylphosphine oxide
  • bis(2,4,6-triethylbenzoyl)-t-butylphosphine oxide
  • bis(2,4,6-triethylbenzoyl)-(2-methyl-prop-1-yl)phosphine oxide
  • bis(2,4,6-triethylbenzoyl)-(1-methyl-prop-1-yl)phosphine oxide
  • bis(2,4,6-triethylbenzoyl)-cyclohexylphosphine oxide
  • bis(2,4,6-triethylbenzoyl)-n-pentylphosphine oxide
  • bis(2,4,6-triethylbenzoyl)-n-hexylphosphine oxide
  • bis(2,4,6-triethylbenzoyl)-(2-ethyl-hex-1-yl)phosphine oxide
  • bis(2,4,6-triethylbenzoyl)-n-octylphosphine oxide
  • bis(2,4,6-triethylbenzoyl)-(2,4,4-trimethyl-pent-1-yl)phosphine oxide
  • bis(2,4,6-triethylbenzoyl)-n-decylphosphine oxide
  • bis(2,4,6-triethylbenzoyl)-phenylphosphine oxide
  • bis(2,6-diethylbenzoyl)-(2,4,4-trimethyl-pent-1-yl)phosphine oxide
  • bis(2,6-diethylbenzoyl)-(2-methyl-prop-1-yl)phosphine oxide
  • bis(2,6-diethylbenzoyl)-n-butylphosphine oxide
  • bis(2,6-diethylbenzoyl)-t-butylphosphine oxide
  • bis(2,6-diethylbenzoyl)-(1-methyl-prop-1-yl)phosphine oxide
  • bis(2,6-diethylbenzoyl)cyclohexylphosphine oxide
  • bis(2,6-diethylbenzoyl)-n-pentylphosphine oxide
  • bis(2,6-diethylbenzoyl)-n-hexylphosphine oxide
  • bis(2,6-diethylbenzoyl)-(2-ethyl-hex-1-yl)phosphine oxide
  • bis(2,6-diethylbenzoyl)-n-octylphosphine oxide
  • bis(2,6-diethylbenzoyl)-phenylphosphine oxide
  • bis(2,4,6-triisopropylbenzoyl)-n-butylphosphine oxide
  • bis(2,4,6-triisopropylbenzoyl)-t-butylphosphine oxide
  • bis(2,4,6-triisopropylbenzoyl)-(2-methyl-prop-1-yl)phosphine oxide
  • bis(2,4,6-triisopropylbenzoyl)-(1 methyl-prop-1-yl)-phosphine oxide
  • bis(2,4,6-triisopropylbenzoyl)-cyclohexylphosphine oxide
  • bis(2,4,6-triisopropylbenzoyl)-n-pentylphosphine oxide
  • bis(2,4,6-triisopropylbenzoyl)-n-hexylphosphine oxide
  • bis(2,4,6-triisopropylbenzoyl)-(2-ethyl-hex-1-yl)-phosphine oxide
  • bis(2,4,6-triisopropylbenzoyl)-n-octylphosphine oxide
  • bis(2,4,6-triisopropylbenzoyl)-(2,4,4-trimethyl-pent-1-yl)-phosphine oxide
  • bis(2,4,6-triisopropylbenzoyl)-n-decylphosphine oxide
  • bis(2,4,6-triisopropylbenzoyl)-phenylphosphine oxide
  • bis(2,4,6-tri-n-butylbenzoyl)-(2-methyl-prop-1-yl)phosphine oxide
  • bis(2,4,6-tri-n-butylbenzoyl)-(2,4,4-trimethyl-pent-1-yl)-phosphine oxide
  • bis(2,4,6-tri-n-propylbenzoyl)-(2-methyl-prop-1-yl)phosphine oxide
  • bis(2,4,6-tri-n-propylbenzoyl)-n-butylphosphine oxide
  • bis(2,4,6-tri-(1-methyl-prop-1-yl)benzoyl)-n-octylphosphine oxide
  • bis(2,4,6-tri-(1-methyl-prop-1-yl)benzoyl)-n-butylphosphine oxide
  • bis(2,4,6-tri-(2-methyl-prop-1-yl)benzoyl)(2,4,4-trimethyl-pent-1-yl)phosphine oxide
  • bis(2,4,6-tri-(2-methyl-prop-1-yl)benzoyl)-(2-methyl-prop-1-yl)phosphine oxide
  • bis(2,4,6-tri-t-butylbenzoyl)-n-butylphosphine oxide
  • bis(2,6-dimethyl-4-n-butylbenzoyl)-(2-methyl-prop-1-yl)phosphine oxide
  • bis(2,6-dimethyl-4-n-butylbenzoyl)-phenylphosphine oxide
  • bis(2,4,6-trimethyl-benzoyl)(2,5-dimethylphenyl)phosphine oxide
  • bis(2,6-dimethyl-4-n-butylbenzoyl)-(2,5-dimethylphenyl)phosphine oxide,
  • bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethyl-pent-1-yl)phoshine oxide and
  • bis(2,6-dichlorobenzoyl)-(4-propylphenyl)phoshine oxide.


Especially preferred photoinitiators are:


Monoacylphosphine oxides such as, for example,


Lucirin TPO (commercially available from BASF) or




  • [Benzyl-(4-morpholin-4-yl-phenyl)-phosphinoyl]-(2,4,6-trimethyl-phenyl)-methanone
    embedded image

    which can be prepared according to the PCT Application PCT-EP02/09045 filed Aug. 13, 2002,

  • [(2-Ethyl-hexyl)-(2,4,4-trimethyl-pentyl)-phosphinoyl](2,4,6-trimethylphenyl)-methanone
    embedded image

    which can be prepared according to the German Patent Publication 10127171 or the British patent GB2365430;

  • 2,4,6-trimethylbenzoyl-phenyl phosphinic acid ethyl ester (BASF).



Bisacylphoshine oxides such as, for example,
embedded image

Irgacure 819, commercially available from Ciba.


Acylphosphine sulfides such as, for example,

  • [phenyl-(2,4,6-trimethyl-benzoyl)-phosphinothioyl]-(2,4,6-trimethyl-phenyl)-methanone
    embedded image

    which can be prepared according to U.S. Pat. No. 5,368,985,
  • or 9-(2,4,6-trimethylbenzoyl)-9-phosphabicyclo[3.3.1]nonane-9-sulfide,
    embedded image

    which can be prepared according to U.S. Pat. No. 5,399,782. Phenylglyoxalates such as, for example Nuvopol 3000 commercially available from Stauffer.
    embedded image


Phenylglyoxalate diester of diols such as Oxo-phenyl-acetic acid 2-[2-(2-oxo-2-phenyl-acetoxy)-ethoxy]-ethyl ester
embedded image

which can be prepared according to U.S. Pat. No. 6,048,660.


The Photoinitiator may be present in an amount from about 0,3-10 wt %, preferably from about 0,3-5 wt %, more preferably from about 1-2 wt %.


Diluent


The residues in the above formula Ia-Ie are defined as follows:


C1-C12Alkyl is linear or branched and is for example C1-C12—, C1-C8—, C1-C6— or C1-C4alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethyl-pentyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl or dodecyl.


The substituted C1-C12alkyl residue may be substituted once or more than once. It is also possible that the substituents are not the same. An example may be a residue like
embedded image

  • A residue of an acrylic acid is —CH═CHCOOH.
  • C1-C6alkoxycarbonyl is for example —C(O)OCH3, —C(O)OCH2CH3.
  • C1-C6alkylaminocarbonyl is for example —C(O)NHCH3.
  • C1-C6alkylcarbonyloxy is for example —O—C(O)CH3.
  • C1-C6alkenylcarbonyloxy is for example —O—C(O)CH═CH2.
  • (Meth)acryloyloxy refers to acryloyloxy (CH2═CH—COO—) or methacryloyloxy (CH2═C(CH3)—COO—).


Phenyl substituted once or more than once by C1C12alkyl is for example —C6H4CH3, —C6H3(CH3)2, —C6H2(CH3)3, —C6H(CH3)4, —C6(CH3)5, —C6H4(CH2)7CH3, —C6H4(CH2)11CH3, —C6H4—C6H11; —C6H4CH(CH3)2, —C6H4C(CH3)3.


Phenyl substituted once or more than once by halogen is for example —C6H4F, —C6H4Cl, —C6H4Br, —C6H4I, —C6H3F2, —C6H3Cl2, —C6H4Br, —C6H4CF3, —C6H3(CF3)2.


Phenyl substituted by C1-C6alkoxycarbonyloxy is for example phenyl substituted by tert.butoxycarbonyloxy (—C6H4OC(O)OC(CH)3).


Phenyl substituted by C1-C6alkylcarbonyloxy is for example phenyl acetate.


Acetylsulfanyl refers to CH3—COS—.


C1-C12alkoxy substituted more than once by fluor is for example —OCH(CF3)2, —O(CF2)7CF3.


Benzyl substituted by a residue selected from an amino butyric acid is for example —C6H4CH2NH(CH2)3COOH—.


Benzyl substituted by C1-C6alkylsulfonyl or C1-C6alkylsulfonium salts, for example —C6H4CH2SO2(CH2)2Cl, or C6H4CH2S+(CH2CH3)2Cl−.


Benzyl substituted by a silanol residue is for example —C6H4CH2CH(Si(OCH2CH3)3))CH3, —C6H4CH2OSi(CH3)3 or —C6H4CH2OSi(CH3)2C(CH3)3.


Benzyl substituted by a residue of a phosphonic acid is for example —C6H4CH2P(O) (OCH2CH3)2.


When Y is O—C1-C12alkylene, wherein the alkylene linker is linear or branched and may be interrupted once or more than once by oxygen, the following linkers may be listed as examples: —O(CH2)3—, —O(CH2)3OC(OH2)3—, —OCH2C(CH2OCH2CH═CH2)(CH2CH3)CH2—.


The group —(CR6R7)m— also includes structures like —CH2CH2CH(CH3)CH2CH2—.


A phthalate residue is for example
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A maleate residue is for example
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C1-C6Alkoxy is likewise linear or branched and is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, iso-butyloxy, tert-butyloxy, pentoxy or hexoxy.


Aryl is for example phenyl, 1-naphthyl, 2-naphthyl, anthracenyl, phenanthryl, in particular phenyl. The aryl residues can be mono or polysubstituted.


Concerning the residue R3, the phenyl ring is preferably para substituted.


Concerning the residue R4, the phenyl ring is preferably unsubstituted or para substituted.


The residue of formula I b is
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Examples for the residue R1-R5 are as follows:

  • R1 —H,
    • —CH3, —CH2CH3, —CH2CH2CH2CH3, —(CH2)5CH3, —(CH2)9CH3,
    • —CH═CHCOOH,
    • —CH2OH, —CH(OH)CH3, —C(CH3)(OH)C≡CH,
    • —CH2OC(O)CH═CH2, —CH2OC(O)C(CH3)═CH2,
    • —CH2OC(O)NHC6H4CH3,
    • —CH2NHCH2CH2CH3,
    • —CH2Cl,
    • —C(O)OCH3, —C(O)OCH2CH3,
    • —C(O)NHCH3,
    • —CHO,
    • —C(O)C6H5,
    • —CN
    • —OH, —OC(O)CH3, —O—C(O)CH═CH2, —O—C(O)C(CH3)═CH2,
    • —Cl
  • R2 —H, —CH3, —CH2CH3, —CH2CH2CH2CH3, —(CH2)5CH3, —(CH2)9CH3,
    • —CH2OH, —CN, —OH, —OC(O)CH3, —Cl
  • R3-1-C10H7, -2C10H7—, C14H9,
    • —C6H4C6H5, —C6H4CH═CH2, —C6H4CH2OH,
    • —C6H4CH3, —C6H3(CH3)2, —C6H2(CH3)3, —C6H1(CH3)4, —C6(CH3)5,
    • —C6H4(CH2)7CH3, —C6H4(CH2)11CH3, —C6H4CH(CH2)5, —C6H4CH(CH3)2, —C6H4C(CH3)3 —C6H4F, —C6H4Cl, —C6H4Br, —C6H4I, —C6F4, —C6H3F2, —C6H3Cl2, —C6H4Br,
    • —C6H4CF3, —C6H3(CF3)2,
    • —C6H4CH2Cl, —C6H4CH2SO2(CH2)2Cl, —C6H4CH2CN,
    • —C6H4CH2CH(Si(OCH2CH3)3))CH3,
    • —C6H4CH2OSi(CH3)3, —C6H4CH2OSi(CH3)2C(CH3)3,
    • —C6H4CH2OC(O)CH3, —C6H4CH2O—C(O)CHCH2,
    • —C6H4CH2O—C(O)C(CH3)CH2,
    • —C6H4CH2OCH2CH(O)CH
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    • —C6H4CH2OC(O)CF3, —C6H4CH2OCH(CF3)2, —C6H4CH2O(CF2)7CF3,
    • —C6H4CH2N(CH3)2, —C6H4CH2N(CH3)3+Cl−, —C6H4CH2NH(CH2)3COOH,
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    • —C6H4CH2P(O)(OCH2CH3)2
    • —C6H4CH2SC(O)CH3, —C6H4CH2S+(CH2CH3)2Cl−, —C6H4CH2SO3−Na+
    • —C6H4CN, —C6H4OH,
    • —C6H4O—C(O)CH═CH2, —C6H4O—C(O)C(CH3)═CH2,
    • —C6H4OC(O)CH3, —C6H4OC(O)OC(CH)3,
    • —C6H4OCH3, —C6H4OCH2CH3, —C6H4OC(CH3)3, —C6H4OC6H5,
    • —C6H3(OCH3)OH, —C6H3(OCH3)2, —C6H3(OCH3)(OCH2C6H5),
    • —CH2—O13 CO—CH═CH2 or —CH2—O—CO—C(CH3)═CH2
  • R4 —H,
    • —CH2OH
    • —CH2OC(O)H
    • —CH2OC(O)CH3, CH2OC(O)C6H5,
    • —CH2OCH3, —CH2OCH2CH3, —CH2OCH2CH2CH3, —CH2OCH2CH2CH3,
    • —CH2OCH2CH2CH2CH3, —CH2OC6H5
    • —CH2O—C(O)CH═CHC(O)OCH2CH═CH2,
    • —CH2OC(O)C6H4C(O)OCH2CH═CH2,
    • —CH2O—C(O)CH═CH2,
    • —CH2OC(O)C(CH3)═CH2,
    • —CH2O(CH2)3O—C(O)CH═CH2,
    • —CH2O(CH2)3O—C(O)C(CH3)═CH2,
    • —CH2O(CH2)3O—C(CH2)3OC(O)CH═CH2,
    • —CH2O(CH2)3OC(CH2)3O—C(O)C(CH3)═CH2,
    • —CH2OCH2C(CH2OCH2CH═CH2)(CH2CH3)CH2O—C(O)C(CH3)═CH2,
    • —CH2CH2O—C(O)CH═CH2,
    • —CH2CH2O—C(O)C(CH3)═CH2,
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    • —CH2CH2CH(CH3)CH2CH2O—C(O)C(CH3)═CH2,
    • —CH2CH2CH(CH3)CH2CH2O—C(O)C(CH2CH3)═CH2,
    • —C6H5, -1-C10H7, -2C10H7, —C14H9,
    • —C6H4C6H5, —C6H4CH═CH2,
    • —C6H4CH3, —C6H3(CH3)2, —C6H2(CH3)3, —C6H1(CH3)4, —C6(CH3)5,
    • —C6H4(CH2)7CH3, —C6H4(CH2)11CH3, —C6H4CH(CH2)5, —C6H4CH(CH3)2, —C6H4C(CH3)3 —C6H4F, —C6H4Cl, —C6H4Br, —C6H4I, —C6F4, —C6H3F2, —C6H3Cl2, —C6H4Br,
    • —C6H4CF3, —C6H3(CF3)2,
    • —C6H5, -1-C10H7, -2-C10H7, —C14H9,
    • —C6H4C6H5, —C6H4CH═CH2,
    • —C6H4CH3, —C6H3(CH3)2, —C6H2(CH3)3, —C6H1(CH3)4, —C6(CH3)5,
    • —C6H4(CH2)7CH3, C6H4(CH2)11CH3, —C6H4CH(CH2)5, —C6H4CH(CH3)2, —C6H4C(CH3)3 —C6H4F, —C6H4Cl, —C6H4Br, —C6H4I, —C6F4, —C6H3F2, —C6H3Cl2, —C6H4Br,
    • —C6H4CF3, —C6H3(CF3)2,
    • —C6H4CH2Cl, —C6H4CH2SO2(CH2)2Cl, —C6H4CH2CN,
    • —C6H4CH2CH(Si(OCH2CH3)3))CH3,
    • —C6H4CH2OH,
    • —C6H4CH2OSi(CH3)3, —C6H4CH2OSi(CH3)2C(CH3)3,
    • —C6H4CH2OC(O)CH3, —C6H4CH2O—C(O)CHCH2,
    • —C6H4CH2O—C(O)C(CH3)CH2,
    • —C6H4CH2OCH2CH(O)CH
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    • —C6H4CH2OC(O)CF3, —C6H4CH2OCH(CF3)2, —C6H4CH2O(CF2)7CF3,
    • —C6H4CH2N(CH3)2, —C6H4CH2N(CH3)3+Cl−, —C6H4CH2NH(CH2)3COOH,
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    • —C6H4CH2P(O)(OCH2CH3)2
    • —C6H4CH2SC(O)CH3, C6H4CH2S+(CH2CH3)2Cl−, —C6H4CH2SO3−Na+
    • —C6H4CN,
    • —C6H4OH,
    • —C6H4O—C(O)CH═CH2, —C6H4O—C(O)C(CH3)═CH2,
    • —C6H4OC(O)CH3, —C6H4OC(O)OC(CH)3,
    • —C6H4OCH3, —C6H4OCH2CH3, —C6H4OC(CH3)3, —C6H4OC6H5,
    • —C6H3(OCH3)OH, —C6H3(OCH3)2, —C6H3(OCH3)(OCH2C6H5),
  • R5 —H, —CH3.


Preferably the compounds of the formula Ia-Ie are those wherein

  • R1 and R2 are hydrogen;
  • R3 is (meth)acryloyloxy-methyl or phenyl para substituted by vinyl,
  • R4 is phenyl or phenyl para substituted by vinyl or (meth)acryloyloxy; or
  •  a substituted phenyl residue of the formula —C6H4CH2—W, wherein W is (meth)acryloyloxy,
  •  or an aliphatic residue of the formula —CH2—Y-A, wherein
    • Y is a bond, O—C1-C12alkylene, wherein the alkylene linker is linear or branched and may be interrupted once or more than once by oxygen,
    • A is hydroxy, C1-C6alkoxy, acetoxy, (meth)acryloyloxy, or a phthalate- or maleate-residue;
  • R5 is hydrogen
  • n is 1;
  • x is —(CH2)—.


More preferably the compounds of the formula Ia-Ie are those wherein

  • R1 and R2 are hydrogen
  • R3 is (meth)acryloyloxy-methyl or phenyl para substituted by vinyl,
  • R4 is phenyl or phenyl para substituted by vinyl;
  •  or an aliphatic residue of the formula —CH2OH, —CH2-(meth)acryloyloxy, —CH2-acetoxy or —CH2—O—C1-C12alkyl or —CH2-A, wherein A is a phthalate- or maleate-residue;
  • R5 is hydrogen
  • n is 1;
  • x is —(CH2)—.


The diluent may be present in an amount of 5 to 50 wt %, preferably 10 to 30 wt %.


Especially preferred compounds of the formula Ia are
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Especially preferred compounds of the formula Ib are the following molecules including their E/Z isomers and regioisomers.
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Especially preferred compounds of the formula Id are:
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Especially preferred compounds of the formula Ie are:
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Preferred Embodiment


A coating composition comprising

  • (1) an alkyd resins,
  • (2) a reactive diluent of the formula Ia-Ie as defined above or mixtures thereof,
  • (3) 0.3 to 10 wt. % of a mono-, bis- or trisacylphosphinoxide photoinitiator of the formula
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  •  wherein
  • X is O or S;
  • R1 and R2 independently of one another are linear or branched C1-C12-alkyl, C1-C12-alkoxy, phenyl, unsubstituted or optionally substituted by OR9, SR9, NR10R11, C1-C12-Alkyl or halogen; or


R1 and R2 are phenyl-C1-C4alkyl or
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  • R3 and R7 independently of one another are C1-C12-alkyl, C1-C12-alkoxy or halogen;
  • R4, R5 and R6 independently of one another are hydrogen, C1-C12-alkyl, C1-C12-alkoxy or halogen;
  • R8, R9 R10 and R11 independently of one another are hydrogen, C1-C12-alkyl, C2C12-alkenyl, benzyl or C2C20-alkyl interrupted once or several times by —O—; or R10 and R11 represent together with the N-atom that they are attached to an optionally oxygen or —NR12-containing 5 or 6 membered ring;
  • R12 is hydrogen, phenyl-C1-C4-alkyl or C1-C12-alkyl.


It is also possible to use mixtures with other known reactive diluents.


Especially suitable is Irgacure 819 (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide).


Additives


The coating composition according to the invention may furthermore contain various additives such as UV stabilizers, cosolvents, dispersants, surfactants, inhibitors, fillers, anti-static static agents, flame-retardant agents, lubricants, antifoaming agents, extenders, plasticizers, anti-oxidants, anti-freezing agents, waxes, thickeners, thixotropic agents, etc. The composition may be used as a clear varnish or may contain pigments. Examples of pigments suitable for use are metal oxides, such as titanium dioxide or iron oxide, or other inorganic or organic pigments.


The coating composition according to the present invention can be applied by conventional methods, including brushing, roll coating, spray coating, or dipping.


Preparation


The compounds of formula Ia-Ie can be prepared starting from the following cycloolefins Ia′-Ie′
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The above cyclo-olefins are reacted in the presence of a metathesis catalyst with a terminal olefin of the formula
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X, R1, R2, R4, R5 are as defined above.


The cyclo-olefins can be prepared by Diels-Alder reactions analogue to the case described for example in WO97/32913.


The following cycloolefins are commercially available.
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Suitable metathesis catalyst are ruthenium, molybdenum or osmium metal carbene complex as for example described in EP0885911A1, EP0839821A2, EP0808338B1, WO93/20111, WO95/07310, WO96/16101, WO97/14738A1, WO97/31913, WO97/38036A1, WO97/32913, WO98/39346A1, WO99/29701 A1, WO99/00397A1 and WO99/00396A1.


Preferred are ruthenium carbenes of the formula (X) with two phosphine ligands and two halogen atoms such as disclosed in WO97/32913.
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wherein

  • T1 and T2 independently of one another are tertiary phosphines, or T1 and T2 together are a tertiary diphosphine;
  • T3 is H, C1-C12alkyl, C3-C6cycloalkyl, C3-C7heterocycloalkyl with one or two heteroatoms selected from the group consisting of —O—, —S— and —N—; C6-C14 aryl, or C4-C15 heteroaryl with one to three heteroatoms selected from the group consisting of —O—, —S— and —N— which are unsubsituted or substituted by C1-C12 alkyl, C1-C12haloalkyl, C1-C12 alkoxy, C6-C10aryl, C6-C10aryloxy, NO2 or halogen;
  • X01 and X02 independently of one another are halogen.


Some specific examples are:

  • Cl2[P(C6H11)3]2Me=CH—C6H5, Cl2[P(C5H9)3]2Me=CH—C6H5, Br2[P(C6H11)3]2Me=CH—C6H5,
  • Br2[P(C5H9)3]2Me=CH—C6H5, F2[P(C6H11)3]2Me=CH—C6H5, F2[P(C5H9)3]2Me=CH—C6H5,
  • Cl2[P(C6H11)3]2Me=CH(C6H4—Cl), Cl2[P(C5H9)3]2Me=CH(C6H4—Br),
  • Br2[P(C6H11)3]2Me=CH(C6H4—NO2), Br2[P(C5H9)3]2Me=CH(C6H4—OC2H5),
  • Cl2[P(C8H11)3]2Me=CH(C6H4—CH3), F2[P(C5H9)3]2Me=CH[C6H3—(CH3)2],
  • Cl2[P(C6H11)3]2Me=CH—C10H9, Cl2[P(C5H9)3]2Me=CH—CH3, Cl2[P(C6H11)3]2Me=CHCH3,
  • Br2[P(C5H9)3]2Me=CH-i-C3H7, Cl2[P(C6H11)3]2Me=CH-t-C4H9, Cl2[P(C5H9)3]2Me=CH-n-C4H9,
  • Cl2[P(C6H11)3]2Me=CH—C6H4—OCH3, Cl2[P(C5H9)3]2Me=CH—C6H3—(CH3)2,
  • Br2[P(C6H11)3]2Me=CH—C6H2—(CH3)3, Br2[P(C5H9)3]2Me=CH—CH2C6H5,
  • Cl2[P(t-C4H9)3]2Me=CH—C6H5, Cl2 [P(i-C3H7)3]2Me=CH—C6H5, Cl2[P(C8H5)3]2Me=CH—C6H5,
  • Cl2[P(C6H3—CH3)3]2Me=CH—C6H5, Br2[P(C5H4(CH3)2)3]2Me=CH—C6H5,
  • Cl2[(C6H3—(CH3)3]2Me=CH—C6H5, Cl2[P(C6H11)3—CH2CH2—P(C6H11)3]Me=CH—C6H5,
  • Cl2[P(C5H9)3]2Me=CH—C6H11, Cl2[P(C5H9)3]2Me=CH—C5H9, C12[P(C5H9)3]2Me=C(C6H11)2,
  • Cl2[P(C6H11)3]2Me=CH2, Cl2[P(C5H9)3]2Me=CH2, Cl2[P(C6H11)3]2Me=CH-nbutyl,
  • Cl2[P(C3H7)3]2Me=CH—C6H5, C12[P(C3H7)3]2Me=CH—C6H11, Cl2[P(i-C3H7)3]2Me=CH—C6H5,
  • Cl2[P(i-C3H7)3]2Me=CH—C5H11.


Also preferred are catalysts as described in WO99/29701 such as, for example,
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The choice of the catalyst is not critical.


Especially preferred is bis-(tricyclohexylphosphin)benzyliden ruthenium-(IV)-dichloride Cl2[P(C6H11)3]2Me=CH—C6H5.


Also preferred is Cl2[P(C3H7)3]2Me=CHS—C6H5.


The metathesis catalyst is used in an amount of 0.005 wt % up to 5 wt %, preferably 0.05 to 0.2 wt %. The Ru-catalyst is removed by absorption on a polar support. After distillation of the volatile reaction by-products, the product of formula I is obtained without any further purification.


Advantageous


The inventive diluents of the formula Ia-Ie can be prepared in one step using ring opening metathesis polymerization. Thus, multifunctional products can be obtained, having a high double bond density, depending on the choice of the reaction parameters.


When using the inventive diluents, it is possible to replace the siccatives by photoinitiators. The inventive coating compositions are storage stable under exclusion of light. Polymerisation occurs only when the compositions are exposed to light. The inventive coating compositions are tack-free after standard radiation curing.


Use


The inventive compositions are especially suitable for use as a decorative or do-it-yourself coating, e.g. for wood substrates, such as door or window frames, but can also be used in industry, in particular for wooden substrates. The coating composition may also be used for substrates made of metal, concrete, plastic materials or other materials.


Furthermore the coatings may be used in sheetfed offset printing inks. These inks preferably contain resin mixtures including alkyd resins. Suitable resin mixtures are: Terlon 3, Sparkl 609, Luminex 11.







EXPERIMENTALS
Example 1
2-Methyl-acrylic Acid 3-(3-vinyl-1,2,3,3a,4,6a-hexahydro-pentalen-1-yl)-allyl Ester

Compound of formula Ib with R4═CH2—Y-A, Y=bond, A is methacryloyloxy.
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A three-neck flask equipped with magnetic stirrer, thermometer and a reflux condenser and equipped for nitrogen flow is flushed with nitrogen. The flask is charged with (19.8 g, 0.15 mol) dicyclopentadiene and with (113.5 g, 0.90 mol) allylmethacrylate. The solution is stirred under nitrogen at room temperature followed by the addition of a solution of 0.5 mol % of bis(tricyclohexylphosphin)benzylidene ruthenium-(IV)-dichloride dissolved in 1.5 ml dichloromethane.


After the exothermic reaction is over, the flask is allowed to cool until reaching room temperature and stirring is carried out for a further 2 hours at room temperature. The progress of the reaction is controlled by gas-chromatography (GC). 200 ml hexane and 15 g bleaching earth (Tonsil AC) are added to the reaction mixture. Stirring is carried out for a further 15 minutes and the solid is filtered off. After evaporation of hexane and surplus allylmethacrylate under vacuum, a colorless oil is obtained (37.7 g, 90% of theory) which, after characterization by 1H-NMR, proves to be the desired compound as major compound. In order to stabilize the oil 1000 ppm HQM (hydroquinone monomethylether) is added.


Example 2
Acetic Acid 3-(3-vinyl-1,2,3,3a,4,6a-hexahydro-pentalen-1-yl)-allyl Ester

Compound of formula Ib with R4═CH2—Y-A, Y=bond, A is acetoxy.
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Acetic acid 3-(3-vinyl-1,2,3,3a,4,6a-hexahydro-pentalen-1-yl)-allyl ester is prepared according to Example 1 using 6.6 g, 0.05 mol dicyclopentadiene and 30.0 g, 0.30 mol allylacetate in the presence of 0.3 mol % bis-(tricyclohexylphosphin)benzylidene ruthenium-(IV)-dichloride. 11.0 g of a low-viscous oil is obtained (99% of theory) which, after characterization by 1H-NMR, contains the reactive diluent as major compound.


Example 3
3-(3-Vinyl-1,2,3,3a,4,6a-hexahydro-pentalen-1-yl)-prop-2-en-1-ol

Compound of formula Ib with R4═CH2—Y-A, Y=bond, A is hydroxy
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3-(3-Vinyl-1,2,3,3a,4,6a-hexahydro-pentalen-1-yl)-prop-2-en-1-ol is prepared according to Example 1 using 6.75 g, 0.051 mol dicyclopentadiene and 17.79 g, 0.30 mol allylalcohol in the presence of 0.3 mol % bis-(tricyclohexylphosphin)benzylidene ruthenium-(IV)-dichloride. 6.34 g of an oil is obtained. After distillation under high vacuum in a ball-tube oven 5.15 g (53%) of a colorless oil is obtained which, after characterization by 1H-NMR, contains the reactive diluent as major compound.


Example 4
1-(3-Butoxy-propenyl)-3-vinyl-1,2,3,3a,4,6a-hexahydro-pentalene

Compound of formula Ib with R4═CH2—Y-A, Y is a bond, A is alkoxy
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1-(3-Butoxy-propenyl)-3-vinyl-1,2,3,3a,4,6a-hexahydro-pentalene is prepared according to Example 1 using 10.7 g, 0.081 mol dicyclopentadiene and 9.2 g, 0.81 mol allylbutylether in the presence of 0.1 mol % bis-(tricyclohexylphosphin)benzylidene ruthenium-(IV)-dichloride. 9.8 g of a colorless oil is obtained (49% of theory) which, after characterization by 1H-NMR, contains the reactive diluent as major compound.


Example 5
But-2-enedioic Acid Allyl Ester 3-(3-vinyl-1,2,3,3a,4,6a-hexahydro-pentalen-1-yl)-allyl Ester

Compound of formula Ib with R4═CH2—Y-A, Y is a bond, A is a maleate residue.
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But-2-enedioic acid allyl ester 3-(3-vinyl-1,2,3,3a,4,6a-hexahydro-pentalen-1-yl)-allyl ester is prepared according to Example 1 using 13.2 g, 0.10 mol dicyclopentadiene and 19.6 g, 0.10 mol diallylmaleaet in the presence of 0.1 mol % bis-(tricyclohexylphosphin)benzylidene ruthenium-(IV)-dichloride. 27.8 g (85% of theory) of a light brown oil is obtained which, after characterization by 1H-NMR, contains the reactive diluent as major compound.


Example 6
Phthalic Acid 1-allyl Ester 2-[3-(3-vinyl-1,2,3,3a,4,6a-hexahydro-pentalen-1-yl)-allyl] Ester

Compound of formula Ib with R4═CH2—Y-A, Y is a bond, A is a phthalate residue
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Phthalic acid 1-allyl ester 2-[3-(3-vinyl-1,2,3,3a,4,6a-hexahydro-pentalen-1-yl)-allyl]ester is prepared according to Example 1 using 13.2 g, 0.10 mol dicyclopentadiene and 24.6 g, 0.10 mol diallylphthalate in the presence of 0.1 mol % bis-(tricyclohexylphosphin)benzylidene ruthenium-(IV)-dichloride. 35.8 g (95% of theory) of a light brown oil is obtained which, after characterization by 1H-NMR, contains the reactive diluent as major compound.


Example 7
1-Styryl-3-vinyl-1,2,3,3a,4,6a-hexahydro-pentalene

Compound of formula Ib with R4=phenyl.
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1-Styryl-3-vinyl-1,2,3,3a,4,6a-hexahydro-pentalene is prepared according to Example 1 using 5.6 g, 0.042 mol dicyclopentadiene and 13.2 g, 0.12 mol styrene in the presence of 0.3 mol % bis-(tricyclohexylphosphin)benzylidene ruthenium-(IV)-dichloride. 7.9 g (79% of theory) of a colorless oil is obtained which, after characterization by 1H-NMR, contains the reactive diluent as major compound.


Example 8
3-Vinyl-1-[2-(4-vinyl-phenyl)-vinyl]-1,2,3,3a,4,6a-hexahydro-pentalene

Compound of formula Ib with R4 is phenyl para substituted by vinyl.
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3-Vinyl-1-[2-(4-vinyl-phenyl)-vinyl]-1,2,3,3a,4,6a-hexahydro-pentalene is prepared according to Example 1 using 6.6 g, 0.05 mol dicyclopentadiene and 19.5 g, 0.15 mol divinylbenzene in the presence of 0.05 mol % bis-(tricyclohexylphosphin)benzylidene ruthenium-(IV)-dichloride. 11.7 g (89% of theory) of a colorless oil is obtained which, after characterization by 1H-NMR, contains the reactive diluent as major compound.


1000 ppm Irganox 1520 are added for stabilisation.


Example 9
1-Vinyl-4-[2-(3-vinyl-cyclopentyl)-vinyl]-benzene

Compound of the formula Ia with R3=phenyl para sunstituted by vinyl.
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1-Vinyl-4-[2-(3-vinyl-cyclopentyl)-vinyl]benzene is prepared according to Example 8 using norbornene and divinylbenzene.


Products with n=2 are for example:
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APPLICATION EXAMPLES

1. Coating Compositions:

Formulation IComparativeAIngredients%%Jagol PS 21 (Ernst Jäger) alkyd resin73.8073.80Exsol D 40 (aliphatic hydrocarbon), solvent21.19—Exkin 2 (methylethylketoxim), anti skinning0.52—Octa-Soligen Calcium 10 (Borchers GmbH) drier0.25—Octa-Soligen Zirkonium 6 (Borchers GmbH)2.33—Octa-Soligen Cobalt 6 (Borchers GmbH)0.62—Octa-Soligen Zink 6 (Borchers GmbH)0.57—Lanco Glidd AH (Lubrizol Coating Additives)0.720.72IRGACURE 819 photoinitiator—2.0reactive diluent—21.19Σ100.0100.0


IRGACURE 819: Bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide

Formulation IIcomparativeAIngredients%%Worléekyd B870, 75% (Worlée Chemie); alkyd80.080.0Varsol D30 (aliphatic hydrocarbon) solvent17.5—Exkin 2 (methylethylketoxim)0.5—Octa-Soligen Calcium 10 (Borchers GmbH)1.0—Octa-Soligen Zirkonium 6 (Borchers GmbH)0.6—Octa-Soligen Cobalt 6 (Borchers GmbH)0.4—Irgacure 819—2.0Reactive diluent—17.5Σ100.0100.0


For evaluation of the drying behavior the above coatings are applied with a 76 μm slit coater to glass and the measurement with the BK-Recorder is started under different light sources at once. A needle is put on the wet film and is pushed with a constant speed of 28 cm/6 h through the film. The record shows five different phases of the drying process within the first 6 hours after application. For evaluation the end of the phases 1 to 4 are listed.

PICTURE 1Different phases of the BK-Recorder measurement.Phase 1No remaining line (wet film)Phase 2Smooth remaining line (increased viscosity of the coating)Phase 3Fringed line (gelation)Phase 4Interrupted line or surface marks (crosslinking)Phase 5No visible marksembedded image


The pendulum hardness is determined at 100 μm on glass plates.


As light sources two fluorescent lamps TL 20 W/03 (Philips; distance: 27 cm), common fluorescent daylight lamps (Hanau 001660 40 W) and diffuse indoor daylight are used.


The viscosity of the formulations is determined by ICI plate-plate viscometer after preparation and different storage time.


Drying Behaviour


Tables 1 and 2 show the drying behavior of the above alkyd systems upon exposure to fluorescent and daylight lamps. The values are given in min.

TABLE 1Formulation ITL03/20 W-lampDaylight lampphasephase12341234Comparative485877113688598184A: diluent Ex. 14831601928144180









TABLE 2










Formulation II










TL03/20 W-lamp
Daylight lamp



phase
phase
















1
2
3
4
1
2
3
4



















Comparative
81
109
150
216
45
141
183
226


A: diluent
17
31
67
202
32
49
77
159


accord. to Ex. 8


A: diluent
6
10
57
90
19
31
81
231


accord. to Ex. 1










Pendulum Hardness


Tab. 3 shows the pendulum hardness upon fluorescent lamps and indoor daylight exposure in the Formulation II.


The use of the reactive diluents and photoinitiator IRGACURE 819 causes a significant increase of the pendulum hardness after one week. The storage stability is good.

TABLE 3pendulum hardness (s)after 168 hoursTL03/20 W-lampDaylightComparative Formulation II3321A: diluent accord. to Ex. 87557A: diluent accord. to Ex. 18450


Comparison of the Reactive Diluents in Formulation II


The formulation containing a diluent according to the invention shows a slightly improved drying behavior. Diallylfumarate, Diethylfumarate and Diallylmaleate do not lead to an increase of the pendulum hardness compared to formulation containing a diluent according to the invention.

TABLE 4drying behavior of formulation II upon daylight lamps.values given in min.phase 1phase 2phase 3phase 4Comparative42160188254Example 1325498158Diethylfumarate365677102Diallylmaleate586884110Diallylfumarate607489113









TABLE 5










pendulum hardness after exposure to indoor


daylight and initial viscosity in Formulation II










Pendulum




hardness (s)
Viscosity (P)
















Exposure time (h)
330
500
0



Comparative
23
25
5.1



Example 1
70
84
7.8



Diethylfumarate
17
18
4.4



Diallylmaleate
15
15
4.2



Diallylfumarate
14
15
4.4










ALTERNATIVE EMBODIMENT

Using mono- or bisacylphosphinoxides as photoinitiators, it has been found that the alkyd coating composition can be cured without any reactive diluent.


Thus, the invention further relates to a coating composition based on an alkyd resin comprising Mapo/Bapo photoinitiators.


In the US-Publication 20020026049 it is stated that Mapo photoinitiators may be suitable as initiators for the curing of oxidatively drying systems without specifying the system. There is no hint to solvent based or water based alkyd coating systems.


It has been found that the siccative and the antiskinning agent can be replaced by using mono-bis- or trisacylphosphinoxides as photoinitiators, thus obtaining a metal free, especially cobalt free and methyl ethyl ketoxime (MEKO) free coating composition.


Cobalt dust and MEKO are both considered to be cancer suspect agents.


Thus, the invention relates to a solvent based or water based alkyd coating composition comprising 0.3 to 10 wt. % of a mono-, bis- or trisacylphosphinoxide photoinitiator of the formula I
embedded image

as describes above.


Preferred are compounds of the formula I′ as describesd above.


Especially preferred are compounds of the formula I′ as described above.


Most preferred is bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.


The invention further relates to the use of a mono-, bis- or trisacylphosphinoxide photoinitiator to cure siccative free and/or anti-skinning agent free alkyd resins.


The invention further relates to a process for curing a solvent based or water based alkyd resin by photochemical treatment with light of a wavelength from 200 to 600 nm.


Definitions and Preferences


Alkyd Resin


Alkyd resins are those as described above.


Solvent


Solvents are aliphatic, cycloaliphatic and aromatic hydrocarbons such as mineral spirits known as white spirit, as well as xylene, toluene, alcohol ethers, glycol ethers, ketones, esters, alcohol ether acetates or mixtures thereof.


As non limiting examples of such solvents may be mentioned toluene, xylene, hydrocarbon solvents available under the trademarks Exsol and Varsol from Exxon Chemicals Co., and solvents such as ethyl acetate, butylacetate, ethyl diglycol, ethyl glycol acetate, butyl glycol, butyl glycol acetate, butyl diglycol, butyl diglycol acetate, and methoxypropylene glycol acetate. Mixtures of solvents may also be used.


Photoinitiators:


Suitable bisacylphosphine oxides and their preparation by oxidation of the corresponding bisacylphosphines are described in EP-B184095 or U.S. Pat. No. 4,737,593.


Preferred bisacylphosphinoxides are those described in U.S. Pat. No. 5,534,559. and listed above.


Especially preferred photoinitiators are:


Monoacylphosphine oxides such as, for example, Lucirin TPO (commercially available from BASF) or

  • [Benzyl-(4-morpholin-4-yl-phenyl)-phosphinoyl]-(2,4,6-trimethylphenyl)-methanone
    embedded image

    which can be prepared according to the PCT Application PCT-EP02/09045 filed Aug. 13, 2002, or
  • [(2-Ethylhexyl)-(2,4,4-trimethyl-pentyl)-phosphinoyl]-(2,4,6-trimethyl-phenyl)-methanone
    embedded image

    which can be prepared according to US-Publication 20020026049 corresponding to the British patent publication GB2365430; or


    2,4,6-trimethylbenzoyl-phenyl phosphinic acid ethyl ester (BASF).


Bisacylphoshine oxides such as, for example,
embedded image

Irgacure 819, commercially available from Ciba.


It is also possible to use


Acylphosphine sulfides such as, for example,

  • [phenyl-(2,4,6-trimethyl-benzoyl)-phosphinothioyl]-(2,4,6-trimethylphenyl)-methanone
    embedded image

    which can be prepared according to U.S. Pat. No. 5,368,985,


    or 9-(2,4,6-trimethylbenzoyl)-9-phosphabicyclo[3.3.1]nonane-9-sulfide,
    embedded image

    which can be prepared according to U.S. Pat. No. 5,399,782.


Especially preferred are bisacylphosphine oxides, for example Irgacure 819 or its dispersion in water (Irgacure 819DW).


Typical amounts of the photoinitiator can be, for example, about 0.3 wt. % to about 10 wt. %, and preferably, about 1 wt. % to about 5 wt. %.


Additives


The coating composition according to the Invention may furthermore contain various additives as described above.


Coating compositions according to the invention can be used for coating precoated or uncoated substrates of wood, metal, plastics, ceramics, concrete, etc.


The coating composition according to the present invention can be applied by conventional methods, including brushing, roll coating, spray coating, or dipping.


APPLICATION EXAMPLES

1. Coating Compositions:

Formulation IComparativeBIngredients%%Jagol PS 21 (Ernst Jäger) alkyd resin73.8073.80Exsol D 40 (aliphatic hydrocarbon), solvent21.1921.19Exkin 2 (methylethylketoxim), anti skinning0.52—Octa-Soligen Calcium 10 (Borchers GmbH) drier0.25—Octa-Soligen Zirkonium 6 (Borchers GmbH)2.33—Octa-Soligen Cobalt 6 (Borchers GmbH)0.62—Octa-Soligen Zink 6 (Borchers GmbH)0.57—Lanco Glidd AH (Lubrizol Coating Additives)0.720.72IRGACURE 819 photoinitiator—2.0Σ100.0100.00


IRGACURE 819: Bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide

Formulation IIcomparativeAIngredients%%Worléekyd B870, 75% (Worlée Chemie); alkyd80.080.0Varsol D30 (aliphatic hydrocarbon) solvent17.517.5Exkin 2 (methylethylketoxim)0.5—Octa-Soligen Calcium 10 (Borchers GmbH)1.0—Octa-Soligen Zirkonium 6 (Borchers GmbH)0.6—Octa-Soligen Cobalt 6 (Borchers GmbH)0.4—Irgacure 819—2.0Σ100.0100.0


For evaluation of the drying behavior the above coatings are applied with a 76 μm slit coater to glass and the measurement with the BK-Recorder is started under different light sources at once. A needle is put on the wet film and is pushed with a constant speed of 28 cm/6 h through the film. The record shows five different phases of the drying process within the first 6 hours after application. For evaluation the end of the phases 1 to 4 are listed.

PICTURE 1Different phases of the BK-Recorder measurement.Phase 1No remaining line (wet film)Phase 2Smooth remaining line (increased viscosity of the coating)Phase 3Fringed line (gelation)Phase 4Interrupted line or surface marks (crosslinking)Phase 5No visible marksembedded image


Drying Behaviour


Tables 1 and 2 show the drying behavior of the above alkyd systems upon exposure to fluorescent and daylight lamps. The values are given in min.

TABLE 1Formulation ITL03/20 W-lampDaylight lampphasephase12341234Comparative485877113688598184B813491713245129141









TABLE 2










Formulation II










TL03/20 W-lamp
Daylight lamp



phase
phase
















1
2
3
4
1
2
3
4



















Comparative
81
109
150
216
45
141
183
226


B
6
13
23
48
31
44
75
107








Claims
  • 1. Compounds of the formula Ia-Ie
  • 2. Compounds of the formula Ia-Ie according to claim 1, wherein R1 and R2 are hydrogen; R3 is (meth)acryloyloxy-methyl or phenyl para substituted by vinyl, R4 is phenyl or phenyl para substituted by vinyl or (meth)acryloyloxy; or  a substituted phenyl residue of the formula —C6H4CH2—W, wherein W is (meth)acryloyloxy, or an aliphatic residue of the formula —CH2—Y-A, wherein Y is a bond, O—C1-C12alkylene, wherein the alkylene linker is linear or branched and may be interrupted once or more than once by oxygen, A is hydroxy, C1-C6alkoxy, acetoxy, (meth)acryloyloxy, or a phthalate or maleate-residue; R5 is hydrogen n is 1; X is —(CH2)—.
  • 3. Compounds of the formula Ia-Ie according to claim 2, wherein R1 and R2 are hydrogen R3 is (meth)acryloyloxy-methyl or phenyl para substituted by vinyl, R4 is phenyl or phenyl para substituted by vinyl;  or an aliphatic residue of the formula —CH2OH, —CH2-(meth)acryloyloxy, —CH2-acetoxy or —CH2—O—C1-C12alkyl or —CH2-A, wherein A is a phthalate or maleate-residue; R5 is hydrogen n is 1; X is —(CH2)—.
  • 4. A compound of the formula Ib according to claim 1.
  • 5. A coating composition comprising (2) an alkyd resin, (3) a reactive diluent of the formula Ia-Ie as defined in claim 1 or mixtures thereof, (3) 0.3 to 10 wt. % of a mono-, bis- or trisacylphosphinoxide photoinitiator of the formula I wherein X is O or S; R1 and R2 independently of one another are linear or branched C1-C12-alkyl, C1-C12-alkoxy, phenyl, unsubstituted or substituted by OR8, SR9, NR10R11, C1-C12-Alkyl or halogen; or R1 and R2 are phenyl-C1-C4-alkyl or R3 and R7 independently of one another are C1-C12alkyl, C1-C12-alkoxy or halogen; R4, R5 and R6 independently of one another are hydrogen, C1-C12-alkyl, C1-C12-alkoxy or halogen; R8, R9 R10 and R11 independently of one another are hydrogen, C1-C12-alkyl, C2C12-alkenyl, benzyl or C2C20-alkyl interrupted once or several times by —O—; or R10 and R11 together with the N-atom to which they are attached form a 5 or 6 membered ring which ring may also contain oxygen atom or atoms or NR12; R12 is hydrogen, phenyl-C1-C4-alkyl or C1-C12-alkyl.
  • 6. Process for preparing compounds of the formula Ia-Ie, wherein a cycloolefin of the formula Ia′-Ie′
  • 7. A decorative or do-it-yourself coating composition according to claim 5, for substrates made of metal, concrete or plastic materials.
  • 8. Solvent-based or water-based alkyd coating composition comprising 0.3 to 10 wt. % of a mono-, bis- or trisacylphosphinoxide photoinitiator of the formula I as defined in claim 5.
  • 9. Solvent-based or water-based alkyd composition according to claim 8, comprising compounds of the formula I′
  • 10. Solvent-based or water-based alkyd composition according to claim 9, comprising compounds of the formula I′,
  • 11. Composition according to claim 10, wherein the photoinitiator is bis(2,4,6-trimethyl benzoyl)-phenylphosphine oxide.
  • 12. A siccative free or antiskinning agent free alkyd resin composition containing 0.3 to 10 wt. % of a mono-, bis- or trisacylphosphinoxide photoinitiator according to claim 8.
  • 13. A process for curing a solvent-based or water-based alkyd resin according to claim 8 by photochemical treatment with light of a wavelength from 200 to 600 nm.
  • 14. A compound of the formula Ib according to claim 2.
  • 15. A compound of the formula Ib according to claim 3.
  • 16. A sheetfed offset print composition according to claim 5.
  • 17. A method of curing siccative free or antiskinning agent free alkyd resins which method comprises adding 0.3 to 10 wt. % of a mono, bis or trisacylphosphinoxide according to claim 8.
Priority Claims (1)
Number Date Country Kind
02405161.7 Mar 2002 EP regional
PCT Information
Filing Document Filing Date Country Kind
PCT/EP03/01899 2/25/2003 WO