WO2004103580A1 - Strongly adherent surface coatings - Google Patents

Strongly adherent surface coatings Download PDF

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Publication number
WO2004103580A1
WO2004103580A1 PCT/EP2004/050806 EP2004050806W WO2004103580A1 WO 2004103580 A1 WO2004103580 A1 WO 2004103580A1 EP 2004050806 W EP2004050806 W EP 2004050806W WO 2004103580 A1 WO2004103580 A1 WO 2004103580A1
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WIPO (PCT)
Prior art keywords
alkyl
phenyl
substituted
unsubstituted
independently
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PCT/EP2004/050806
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French (fr)
Inventor
Jean-Pierre Wolf
Martin Kunz
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Ciba Specialty Chemicals Holding Inc.
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Application filed by Ciba Specialty Chemicals Holding Inc. filed Critical Ciba Specialty Chemicals Holding Inc.
Priority to US10/556,609 priority Critical patent/US20060257681A1/en
Priority to MXPA05012091A priority patent/MXPA05012091A/en
Priority to EP04741574A priority patent/EP1628778B1/en
Priority to CA002522898A priority patent/CA2522898A1/en
Priority to DE602004005981T priority patent/DE602004005981T8/en
Priority to JP2006530197A priority patent/JP5008978B2/en
Publication of WO2004103580A1 publication Critical patent/WO2004103580A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • 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
    • 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
    • C08F290/08—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 side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B05D3/067—Curing or cross-linking the coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/068—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using ionising radiations (gamma, X, electrons)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/08—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by flames
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141—Plasma treatment
    • B05D3/142—Pretreatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12556—Organic component
    • Y10T428/12569—Synthetic resin

Definitions

  • the invention relates to a process for the production of coatings having good adherence on inorganic or organic substrates, wherein a low-temperature plasma treatment, a corona discharge treatment or a flame treatment is carried out on the inorganic or organic substrate, a specific photoinitiator or a plurality of photoinitiators is applied to the inorganic or organic substrate, and the substrate so precoated with photoinitiator is provided with a further coating.
  • the invention relates also to the use of certain photoinitiators in the production of such layers and to the strongly adherent coatings themselves.
  • adhesion properties of coatings e.g. finishes, paints, printing inks or adhesives
  • inorganic or organic substrates especially on non-polar substrates such as polyethylene, polypropylene or fluorine-containing polyolefins
  • primers special priming coatings
  • a further possibility lies in exposing the substrates to be coated to a plasma treatment or corona treatment and then coating them, it being possible for a grafting process with e.g. acrylate monomers to be carried out between those two operations (J. Polym. ScL, Part A: Polym. Chem. 31 , 1307-1314 (1993)).
  • a strongly adherent coating layer is obtained by adding a suitable coinitiator to the coating being applied.
  • MAPO monoacylphosphine oxide
  • WO 99/47185 WO 00/55212 and WO 00/55214 the above-described vinyl MAPOs are used for the preparation of UV-crosslinkable copolymers for contact lens manufacture.
  • coatings of photocurable compositions having especially good adherence can be obtained by applying a certain photoinitiator to a substrate to be coated, after that substrate has been subjected to a plasma treatment (low pressure and/or normal pressure plasmas), corona treatment or flame treatment, and drying and/or irradiating the substrate so treated.
  • the substrates so pretreated are provided with a coating and cured.
  • the resulting coatings exhibit surprisingly good adhesion which does not suffer any appreciable deterioration even after several days' storage or exposure to sunlight.
  • the invention relates to a process for the production of a strongly adherent coating on an inorganic or organic substrate, wherein a) a low-temperature plasma treatment, a corona discharge treatment or a flame treatment is carried out on the inorganic or organic substrate, b) one or more photoinitiators or mixtures of photoinitiators with monomers or/and oligomers, containing at least one ethylenically unsaturated group, or solutions, suspensions or emulsions of the afore-mentioned substances, are applied to the inorganic or organic substrate, and optionally c) using suitable methods those afore-mentioned substances are dried and/or are irradiated with electromagnetic waves, wherein there is used as photoinitiator at least one compound of formula (I), (II), (III) and/or (IV)
  • IN and IN 1 are each independently of the others a monacylphosphine, monoacylphosphine oxide or monoacylphosphine sulfide photoinitiator group;
  • initiator group IN or IN 1 has, for example, the following structure A-C-P— , wherein
  • R is C ⁇ -C 24 alkyl unsubstituted or substituted by C 3 -C 24 cycloalkyl, C 3 -C 24 cycloalkenyl, phenyl, CN, C(0)Rn, C(0)OR ⁇ , C(0)N(R 14 ) 2 , OC(0)Rn, 0C(O)0Rn, N(R 14 )C(0)N(R M ), OC(0)NR 14 , N(R 14 )C(0)0R ⁇ , halogen, ORn, SR-n or by N(R 12 )(R 13 ); or R is C 2 -C 24 alkyl interrupted one or more times by non-consecutive O or S and unsubstituted or substituted by phenyl, ORn, CN, C(0)Rn, C(0)ORn or by C(0)N(R 14 ) 2 ; or R is C 2 -C 24 alkenyl uninterrupted or interrupted one or more times by non-consecutive O and unsubstitute
  • R is , C 8 -C 24 arylcycloalkyl or C 8 -C 24 arylcycloalkenyl
  • Re, R7, Ra, ⁇ and R1 0 are each independently of the others hydrogen, CrC 24 alkyl unsubstituted or substituted by SRn, N(R-
  • R 11 is hydrogen, CrC 2 oalkyl, C 2 -C 2 oalkenyl, C 3 -C 8 cycloalkyl, benzyl; or Rn is C 2 -C 2 oalkyl interrupted one or more times by O, or C 2 -C 2 oalkenyl interrupted one or more times by O; or Rn is phenyl unsubstituted or substituted by CrC 4 alkyl or by C C alkoxy; R 12 and R 13 are each independently of the other hydrogen, CrC 2 oalkyl, C 2 -C 20 alkenyl, C 3 -C 8 cycloalkyl or benzyl; or R ⁇ 2 and R « are C 2 -C 2 oalkyl interrupted one or more times by O, or C 2 -C 2 oalkenyl interrupted one or more times by O; or R 12 and R 13 are phenyl unsubstituted or substituted by C C 4 alkyl or by CrC 4 alk
  • R M is hydrogen, C ⁇ -C ⁇ _alkyl; phenyl unsubstituted or substituted by C ⁇ -C 4 alkyl or by CrC 4 - alkoxy, or benzyl unsubstituted or substituted by C ⁇ -C 4 alkyl or by CrC aIkoxy, or R 14 is C 2 -C 12 alkyl interrupted one or more times by O.
  • L, Lt and L 2 as a spacer group are, for example, a radical -Z-[(A 1 ) a -Y] c -[(A 2 ) b -X
  • X, Y and Z are each independently of the others a single bond, -0-, -S-, -N(R ⁇ 6 )-, -(CO)-,
  • R 16 is hydrogen, CrC ⁇ 2 alkyl or phenyl.
  • RGi and RG 2 are each independently of the other . and R d , R ⁇ and f are each independently of the others hydrogen, C ⁇ -C 4 alkyl, phenyl, (CO)0-(C ⁇ -C 4 alkyl) or d-dalkylphenyl.
  • C ⁇ -C 24 Alkyl is linear or branched and is, for example, d-do-, C Ci 2 -, C C 8 -, CrC 6 - or C ⁇ -C 4 -alkyl.
  • Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert- butyl, pentyl, hexyl, heptyl, 2,4,4-trimethyl-pentyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and icosyl.
  • C 2 -C 24 Alkyl interrupted one or more times by non-consecutive O, S or NR M is linear or branched, preferably linear, and is interrupted, for example, 1 -9 times, e.g. 1-7 times or once or twice by O, S or NR ⁇ 4 .
  • the radicals are interrupted by more than one 0, the O atoms are separated from one another by at least one methylene group.
  • C 2 -C 24 Alkenyl radicals may be mono- or poly-unsaturated, and also linear or branched and are, for example, C 2 -C 2 )-, C 2 -C 8 -, C 2 -C 6 -, C 4 -C 8 -, C -C 6 -, C ⁇ -C ⁇ - or C 2 -C -alkenyl.
  • Examples are vinyl, allyl, methallyl, 1,1-dimethylallyl, 1-butenyl, 2-butenyl, 1,3-pentadienyl, 1-hexenyl, 1- octenyl, decenyl and dodecenyl, especially allyl.
  • Examples of 0-, S- or N-containing 5- or 6-membered heterocyclic rings are furyl, thienyl, pyrrolyl, oxinyl, dioxinyl and pyridyl.
  • the mentioned heterocyclic radicals can be mono- or poly-substituted, for example mono- or di-substituted, by linear or branched alkyl, e.g. methyl, ethyl, propyl, butyl, pentyl or hexyl, especially C ⁇ -C 4 alkyl. Examples thereof are dimethyl- pyridyl, dimethyl pyrrolyl and methylfuryl.
  • Substituted phenyl is mono- to penta-substituted, e.g. mono-, di- or tri-substituted, especially mono- or di-substituted on the phenyl ring.
  • Halogen is fluorine, chlorine, bromine and iodine, especially chlorine and bromine, preferably chlorine.
  • O or by NR 14 they are, for example, saturated or unsaturated rings, for example cyclopentyl, cyclohexyl, aziridinyl, pyrrolyl, pyrrolidinyl, oxazolyl, thiazolyl, pyridyl, 1,3-diazinyl, 1,2-diazinyl, piperidyl or morpholinyl.
  • saturated or unsaturated rings for example cyclopentyl, cyclohexyl, aziridinyl, pyrrolyl, pyrrolidinyl, oxazolyl, thiazolyl, pyridyl, 1,3-diazinyl, 1,2-diazinyl, piperidyl or morpholinyl.
  • Cycloalkyl is linear or branched alkyl that contains at least one ring or consists solely of one ring, for example cyclopropyl, cyclopentyl, methylcyclopentyl, cyclohexyl, methyl- or dimethyl-cyclohexyl, cyclooctyl or cyclododecyl, especially cyclopentyl and cyclohexyl.
  • Cycloalkyl is as defined above up to the appropriate number of carbon atoms.
  • cycloalkyl is to be understood as including bridged systems, such as, for exampl
  • Cycloalkyl uninterrupted or interrupted one or more times by non-consecutive O, S or NR 14 is likewise, as described above, linear or branched alkyl that contains at least one ring or consists solely of one ring and is, for example, - ⁇ ° , ⁇ T ⁇ , V ⁇ N ?" , ' 'Tpc— ,
  • Cycloalkenyl and C 5 -C 2 4cycloalkenyl correspond to the meanings given above for cycloalkyl, but the ring in question contains at least one double bond.
  • the term also includes polyunsaturated rings and also bridged rings, e.g. cyclopropenyl, cyclopentenyl, methylcyclopentenyl, cyclohexenyl, methyl- or dimethyl-cyclohexenyl, cyclooctenyl or cyclo- dodecenyl, especially cyclopentenyl and cyclohexenyl.
  • Aryl alkyl is alkyl substituted by an aromatic radical. Examples are phenyl-C ⁇ -C ⁇ 8 alkyl, naphthyl-d-C ⁇ 6 alkyl, anthryl-C C 10 alkyl, phenanthryl-d-C 10 alkyl, wherein the respective alkyl radical C ⁇ -C ⁇ 8 -, C 1 -C1 6 -, d-C ⁇ 0 - is substituted by the respective aromatic radical phenyl, naphthyl, anthryl or phenanthryl.
  • the alkyl radicals are linear or branched and can have the meanings given above.
  • Examples are benzyl, phenylethyl, ⁇ -methylbenzyl, phenylpentyl, phenylhexyl and ⁇ , ⁇ -dimethylbenzyl, especially benzyl, naphthylmethyl, naphthylethyl, naphthylpropyl and naphthyl-1-methylethyl, more especially naphthylmethyl.
  • the alkyl moiety may be in either the 1- or the 2- ⁇ osition of the naphthyl ring.
  • Arylcycloalkyl is cycloalkyl substituted by an aromatic radical and is, for example, Cg-C ⁇ 6 arylcycloalkyl, C 9 -C ⁇ 3 aryIcycloalkyl, e.g. cycloalkyl bonded to one or more rings, for
  • At least one is intended to define “one or more than one”, e.g. one or two or three, preferably one or two.
  • A is preferably .
  • Ri and R are preferably .
  • R 2 are C C 4 alkyl, especially methyl, or CrC 4 alkoxy, especially methoxy.
  • A is, for example, 2,4,6-trimethyl phenyl or 2,6-dimethoxyphenyl.
  • Ri and R 2 are each independently of the other C ⁇ -C ⁇ 2 alkyl, ORn, CF 3 or halogen, especially d-C alkyl, C ⁇ -C 4 alkoxy, CF 3 or Cl;
  • R 3 , R and R 5 are each independently of the others hydrogen, C ⁇ -C 12 alkyl, ORn or halogen, especially hydrogen or C ⁇ -C alkyl.
  • the radical R can be aliphatic or aromatic.
  • an aliphatic radical R is preferably
  • R is C 2 -C ⁇ 2 alkyl interrupted one or more times by non -consecutive O and unsubstituted or substituted by phenyl, CN, ORn, C(0)Rn, C(0)ORn or by C(0)N(R 14 ) 2 ; or R is C 2 -C ⁇ 2 alkenyl uninterrupted or interrupted one or more times by non -consecutive O and unsubstituted or substituted additionally by ORn, N(R ⁇ 2 )(R 13 ) or by C ⁇ -C ⁇ 2 alkyl; or R is benzyl; or R is C 4 -C 8 cycloalkyl uninterrupted or interrupted one or more times by non -consecutive
  • R is C 8 -C ⁇ 2 arylcycloalkyl
  • R 11 is hydrogen, d-d ⁇ alkyl, C 5 -C 6 cycloalkyl, phenyl or benzyl;
  • R 12 and R 13 are each independently of the other hydrogen, Crd 2 alkyl, phenyl, benzyl, or
  • R14 is hydrogen, phenyl, C ⁇ -Ci 2 alkyl, or C 2 -C ⁇ 2 alkyl interrupted one or more times by non- consecutive O atoms and unsubstituted or substituted by OH or by SH.
  • R is preferably C ⁇ -C ⁇ 2 alkyl.
  • R is preferably , wherein
  • R 6 , R 7 , R 8 , Rg and R10 are each independently of the others hydrogen, C ⁇ -C ⁇ 2 alkyl, ORn, phenyl or halogen, especially C ⁇ -C 4 alkyl; d-C 4 alkoxy, phenyl or Cl.
  • R d , R ⁇ and R f are each independently of the others hydrogen, phenyl, (CO)0-(C C 4 alkyl), for example especially (CO)OC 2 H 5 .
  • A, R, L and RG are as defined above;
  • Hal is a halogen atom, especially Br, 1 or Cl;
  • M is an alkali metal, for example Li, Na, K.
  • corresponding metallated starting materials are obtained selectively, for example, by reaction of acyl halides with dimetallated arylphosphines: o o
  • the dimetallated phosphine is obtained by reaction of the corresponding dichloride with the metal.
  • a further possibility lies in reacting the corresponding phosphine with, for example, organolithium compounds, for example butyl lithium. The reactions are described in detail in the publications mentioned above.
  • A, R, L and RG are as defined above; Hal is a halogen atom, especially Br, I or Cl.
  • the invention relates likewise to compounds of formulae (F), (IP), (IIP) and (IV)
  • IN and IN 1 are each independently of the others a monoacylphosphine, monoacylphosphine oxide or monoacylphosphine sulfide photoinitiator group;
  • Q, Q1 and Q 2 are a single bond or a spacer group of formula — Z ⁇ -[(A 1 ) a -Y] c -[(A 2 )b-X]d-,
  • X and Y are each independently of the other a single bond, -0-, -S-, -N(R ⁇ 6 )-, -(CO)-, -(CO)O-, -(CO)N(R 1 ⁇ )-, -O-(CO)-, -N(R 1 ⁇ )-(CO)- or -N(R 16 )-(CO)0-;
  • Z 1 is a single bond, -S-, -(CO)-, -(CO)O-, -(CO)N(R ⁇ ⁇ )-, -O-(CO)-, -N(R 16 )-(CO)- or -N(R 16 )-(CO)0-;
  • a ! and A 2 are each independently of the other C ⁇ -C ⁇ 2 alkylene, C 3 -C 12 cycloalkylene, phenyl- ene, phenylene-C ⁇ -C 4 alkylene or C ⁇ -C 4 alkyIene-phenylene-C ⁇ -C alkylene; a, b, c and d are each independently of the other a number 0 to 4; R 16 is hydrogen, CrC 1 alkyl or phenyl;
  • photoinitiators of the mono- and bis-acylphosphine oxide type such as published in WO 03/068785.
  • the invention therefore relates also to a process for the production of a strongly adherent coating on an inorganic or organic substrate, wherein a) a low-temperature plasma treatment, a corona discharge treatment or a flame treatment is carried out on the inorganic or organic substrate, b) one or more photoinitiators or mixtures of photoinitiators with monomers or/and oligomers, containing at least one ethylenically unsaturated group, or solutions, suspensions or emulsions of the afore-mentioned substances, are applied to the inorganic or organic substrate, and optionally c) using suitable methods those afore-mentioned substances are dried and/or are irradiated with electromagnetic waves, wherein there is used as photoinitiator at least one compound of formula (XX) and/or (X
  • R 70 and R 7 ⁇ are each independently of the other CrC ⁇ 8 alkyl, C 2 -d 8 alkyl uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or by one or more substituted or unsubstituted imino groups, C 2 -d 8 alkenyl, C 6 -C ⁇ 2 aryl, C 5 -d 2 cycloalkyl or a five- to six- membered heterocycle having oxygen, nitrogen and/or sulfur atoms, wherein the mentioned radicals may each be substituted by aryl, alkyl, aryloxy, alkyloxy, hetero atoms and/or by heterocycles;
  • E 2 is O, S, NR 72 , N-OR 3 or N-NR 72 R 7 3;
  • Ei is O, S, NR 72 , N-OR 72 , N-NR 72 R 73 or a free electron pair;
  • R 72 is hydrogen, C ⁇ -C 4 alkyl, S0 3 H, phenyl or acetyl;
  • R 73 is hydrogen, d-C 4 alkyl, C00R 72 , or C ⁇ -C ⁇ 2 aryl or arylsulfonyl unsubstituted or substituted by aryl, alkyl, aryloxy, alkyloxy, hetero atoms and/or by heterocycles;
  • L is a spacer
  • RG 3 is a free-radical-polymerisable or cationically polymerisable group or a group capable of interacting with the polymer being formed; m is a natural number from 1 to 10;
  • R7 0 ', R7 E 2 ' and E1' are as defined for R 70> R 7 ⁇ , E 2 and E1 but may be different therefrom;
  • Heti and Het 2 are each independently of the other O, S or NR 4 ;
  • R 74 are, identical or different, hydrogen or d-C 4 alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
  • the spacer L has, for example, the meanings given above.
  • RG 3 is preferably identical to the group RG described above.
  • the process according to the invention is simple to carry out and allows a high throughput per unit of time, since lengthy application steps and slow crosslinking reactions are not required.
  • the process is especially well suited to workpieces that are composed of different plastics and/or metals or types of glass and that without the pretreatment would therefore exhibit different degrees of adhesion on the different components or that in the case of a conventional primer treatment exhibit different affinities for the primer.
  • the photoinitiator can be applied, for example, at normal pressure - preferably after a corona treatment in a first process step, or, for example, vapour-deposited in vacuo, preferably after a plasma treatment in the first process step.
  • a fixing step for the photoinitiator is carried out by exposure to UV/VIS light.
  • drying includes both variants, both the removal of the solvent and the fixing of the photoinitiator.
  • a process for the production of a strongly adherent coating on inorganic or organic substrates wherein a) a low-temperature plasma treatment, a corona discharge treatment or a flame treatment is carried out on the inorganic or organic substrate, b) one or more photoinitiators of formula (I), (II), (III) and/or (IV) or mixtures of such photoinitiators with monomers or/and oligomers, containing at least one ethylenically unsaturated group, or solutions, suspensions or emulsions of the afore-mentioned substances, are applied to the inorganic or organic substrate, and c) using suitable methods those afore-mentioned substances are optionally dried and irradiated with electromagnetic waves to fix the photoinitiator.
  • Step c) of the above-described preferred processes is optional.
  • the drying that is to say the removal of the solvent, is logically unecessary when no solvent has been used.
  • the fixing of the photoinitiator in step c) of the preferred processes by irradiation with electromagnetic waves, especially UV ⁇ /IS radiation is also optional. In a preferred embodiment of the process, however, the fixing of the photoinitiator by irradiation with electromagnetic waves, especially UV ⁇ /IS radiation, is carried out.
  • the invention relates also to a process for the production of a strongly adherent coating on an inorganic or organic substrate, wherein a) a low-temperature plasma treatment, a corona discharge treatment or a flame treatment is carried out on the inorganic or organic substrate, b) one or more photoinitiators of formula (I), (II), (III) and/or (IV) according to claim 1 or mixtures of such photoinitiators with monomers or/and oligomers, containing at least one ethylenically unsaturated group, or solutions, suspensions or emulsions of the aforementioned substances, are applied to the inorganic or organic substrate, optionally c) using suitable methods those afore-mentioned substances are dried and/or irradiated with electromagnetic waves and either d1) the substrate so precoated with photoinitiator is coated with a composition comprising at least one ethylenically unsaturated monomer or oligomer and the coating is cured by means of UV
  • the substrate so precoated with photoinitiator is provided with a coating and dried; or d3) a metal, semi-metal, metal oxide or semi-metal oxide is deposited from the gaseous phase onto the substrate so precoated with photoinitiator.
  • Process step b) in each of the above-described processes is preferably carried out under normal pressure.
  • the invention relates also to a process according to either claim 1 or claim 2 wherein in addition to the compounds of formula (I), (II), (III) and/or (IV) there are used further photoinitiators (p).
  • further photoinitiators (p) that can be applied in addition to the compounds of formula (I), (II), (111) and/or (IV), or in addition to the compounds of formula (XX) and/or (XXI) in process step (b), there are suitable in principle any compounds and mixtures that form one or more free radicals when irradiated with electromagnetic waves.
  • These include initiator systems consisting of a plurality of initiators and systems that function independently of one another or synergistically.
  • sensitisers for example acridines, xanthenes, thiaze ⁇ es, coumarins, thioxanthones, triazines and dyes.
  • sensitisers for example acridines, xanthenes, thiaze ⁇ es, coumarins, thioxanthones, triazines and dyes.
  • Such compounds and derivatives are derived, for example, from the following classes of compounds: benzoins, benzil ketals, acetophenones, hydroxyalkylphenones, aminoalkyl- phenones, acylphosphine oxides, acylphosphine sulfides, acyloxyiminoketones, alkylamino- substituted ketones, such as Michler ' s ketone, peroxy compounds, dinitrile compounds, halogenated acetophenones, phenylglyoxalates, dimeric phenylglyoxalates, benzophen- ones, oximes and oxime esters, thioxanthones, coumarins, ferrocenes, titanocenes, onium salts, sulfonium salts, iodonium salts, diazonium salts, borates, triazines, bisimidazoles, polysilanes and dyes. It
  • additional photoinitiators (p) are compounds of formula V, VI, VII, VIII, IX, X or/and XI
  • R 29 is hydrogen or C ⁇ -C ⁇ 8 alkoxy
  • R ⁇ is hydrogen, C ⁇ -C 18 alkyl, C ⁇ -C ⁇ 8 alkoxy, -OCH 2 CH 2 -OR 47 , morpholino, SCH 3 , or a group
  • a, b and c are an average of 3; n is a value of from 2 to 10;
  • G and G 4 are each independently of the other terminal groups of the polymeric unit, especially hydrogen or CH 3 ;
  • R 31 is hydroxy, C ⁇ -C ⁇ 6 alkoxy, morpholino, dimethylamino or -0(CH 2 CH 2 0) m -C Ci 6 alkyl;
  • R 32 and Rss are each independently of the other hydrogen, C C ⁇ alkyl, CrC 16 alkoxy or -0(CH 2 CH 2 ⁇ ) m -C ⁇ -C ⁇ 6 alkyl; or
  • R 32 and R 33 are phenyl or benzyl, those radicals being unsubstituted or substituted by C C ⁇ 2 alkyl; or R 32 and R 33 , together with the carbon atom to which they are bonded, form a cyclohexyl ring;
  • m is a number from 1 to 20; but R 31 , R 32 and R M are not all simultaneously C C 18 alkoxy or -0(CH 2 CH 2 0) m -CrC 16 alkyl;
  • R M , 36 , R 37 and R 38 are each independently of the others hydrogen or methyl;
  • RK and R 3 ! 3 are hydrogen, methyl or phenylthio, wherein the phenyl ring of the phenylthio radical is unsubstituted or substituted in the 4-, 2-, 2,4- or 2,4,6-position(s) by C C 4 alkyl;
  • R 4 0 and R 41 are each independently of the other CrC 20 alkyl, cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenylyl, those radicals being unsubstituted or substituted by halogen, C C ⁇ 2 alkyl, d-C 12 alkoxy, C C ⁇ 2 alkylthio or by NR 52 R 53 .
  • R 40 and R 41 are a S- or N- containing 5- or 6-membered heterocyclic ring or -(CO)R 42 ;
  • R 42 is cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenylyl, those radicals being unsubstituted or substituted by halogen, d-dalkyl or/and by Crdalkoxy, or R 2 is a S- or N- containing 5- or 6-membered heterocyclic ring;
  • R 43 and R 4 are each independently of the other cyclopentadie ⁇ yl unsubstituted or mono-, di- or tri-substituted by C ⁇ -C ⁇ 8 alkyl, d-C ⁇ 8 alkoxy, cyclopentyl, cyclohexyl or by halogen;
  • R 4 5 and R4 6 are each independently of the other phenyl which is substituted by fluorine atoms or CF 3 in at least one of the two positions ortho to the titanium-carbon bond and may contain, as further substituents at the aromatic ring, polyoxaalkyl or pyrrolinyl unsubstituted or substituted by one or two C ⁇ -Ci 2 alkyl, di(C ⁇ -Ci 2 alkyl)aminomethyl, morpholinomethyl, C 2 -C 4 alkenyl, methoxy methyl, ethoxymethyl, trimethylsilyl, formyl, methoxy or phenyl substituents,
  • R 48 , 49 and R 50 are each independently of the others hydrogen, halogen, C 2 -Ci 2 alkenyl, d-C ⁇ 2 alkoxy, C 2 -C 12 alkoxy interrupted by from one to four O atoms, cyclohexyloxy, cyclopentyloxy, phenoxy, benzyloxy, or phenyl or biphenylyl each unsubstituted or substituted by d-dalkoxy, halogen, phenylthio or by -dalkylthio, wherein R 48 and R 5 o are not both simultaneously hydrogen and in the radical
  • At least one radical R4 8 or R 50 is C ⁇ -C ⁇ 2 alkoxy, C 2 -C ⁇ 2 alkoxy interrupted by from one to four O atoms, cyclohexyloxy, cyclopentyloxy, phenoxy or benzyloxy;
  • G 5 is O, S or NR 5 ⁇ ;
  • Rs- ⁇ is C C 8 alkyl, phenyl or cyclohexyl
  • R 52 and Rs 3 are each independently of the other hydrogen; Ci-Caalkyl uninterrupted or interrupted by O atoms and unsubstituted or substituted by OH or by SH; or R 52 and R 53 are
  • R M is hydrogen, or a group ;
  • R 55 , ⁇ s, R 5 7 1 R 58 and R 59 are each independently of the others hydrogen; Ci-Caalkyl which is unsubstituted or substituted by OH, d-C 4 alkoxy, phenyl, naphthyl, halogen or by CN and may be interrupted by one or more O atoms; or R 55 , R x , R 5 , Rs ⁇ and Rsg are d-dalkoxy, d-dalkylthio or NR 52 R53;
  • Y ! is a divalent aliphatic or aromatic radical, especially C ⁇ -d 2 alkylene; x is 0 or 1 ;
  • R ⁇ is phenyl, naphthyl, or, when x is 0, 9H-carbazol-3-yl, or (9-oxo-9H-thioxanthe ⁇ -2-yl)-, all those radicals being unsubstituted or substituted by one or more SRe 3 , ORw, NR 52 R 53 , halogen, Ci-Caalkyl, phenyl, benzyl, -(CO)-CrC 4 alkyl, -(CO)-phenyl or -(CO)-phenylene- C ⁇ -C 4 alkyl substituents; ei is C 4 -C 9 cycloalkanoyl; d-C ⁇ alkanoyl unsubstituted or substituted by one or more halogen, phenyl or CN substituents; or R 6 ⁇ is C 4 -C ⁇ alkenoyl, with the proviso that the double bond is not conjugated with the carbonyl group; or R
  • R 82 is hydrogen, phenyl or benzoyl, the radicals phenyl and benzoyl being unsubstituted or substituted by C ⁇ -C 6 alkyl, phenyl, halogen, OR 6 4, SR ⁇ or by NR 52 R S3 ; or R 62 is Ci-Caalkyl or C 2 -C ⁇ 2 alkoxycarbonyl, the radicals d-C 2 oalkyl and C 2 -Ci 2 alkoxycarbonyl being unsubstituted or substituted by OH and uninterrupted or interrupted by one or more O atoms; or R 6 is
  • Rra and R 6 are each independently of the other hydrogen or CrC ⁇ 2 alkyl unsubstituted or substituted by OH, SH, CN, phenyl, (CO)0-C ⁇ -C 4 alkyl, 0(CO)-C ⁇ -C 4 aIkyl, COOH, O(CO)- phenyl, and such unsubstituted or substituted C ⁇ -C 12 alkyl may be interrupted by one or more O atoms; or Rr ⁇ and R 6 4 are cyclohexyl, or phenyl unsubstituted or substituted by
  • R ⁇ and R 67 are each independently of the others hydrogen, CrC 4 alkyl, d-C 4 haloalkyl,
  • Res is hydrogen, C ⁇ -C 4 alkyl, d-C haloalkyl, phenyl, N(d-C 4 alkyl) 2 , COOCH 3 , o u or - -0O--CC--cC --0O--((CCHH 22 )) 44 -- --0O--CC--CC--0O ⁇ c ⁇ ; or R B8 and R 67 together are -S-. H, i - J ⁇ H, xxo
  • C C 2 oAlkyl has the meanings given above up to the appropriate number of carbon atoms.
  • C ⁇ -C ⁇ 8 Alkoxy is, for example, branched or unbranched alkoxy, e.g. methoxy, ethoxy, n- propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2,4,4-trimethyl-pent-1-yloxy, 2-ethyl hexyloxy, nonyloxy, decyloxy, dodecyloxy or octadecyloxy.
  • C C ⁇ 6 -, C ⁇ -C 12 - and C ⁇ -C 4 -alkoxy have the meanings given above up to the respective number of carbon atoms.
  • C ⁇ -C ⁇ Alkylthio is linear or branched and is, for example, C ⁇ -C 8 -, C ⁇ -C 6 - or C ⁇ -C 4 -a]kylthio, for example methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec- butylthio or tert-butylthio, preferably methylthio.
  • Substituted phenyl is, for example, mono- to penta-substituted, for example mono-, di- or tri- substituted, on the phenyl ring.
  • R 40 , R 41 and R 42 are a S- or N-containing 5- or 6-membered heterocyclic ring, they are, for example, thienyl, pyrrolyl or pyridyl.
  • C 2 -Ci 2 Alkenyl is linear or branched, can be mono- or poly-unsaturated and is, for example, allyl, methallyl, 1,1-dimethylallyl, 1-butenyl, 2-butenyl, 1,3-pentadienyl, 1-hexenyl or 1-octenyl, especially allyl.
  • C 2 -C 4 Alkenyl is, for example, allyl, methallyl, 1-butenyl or 2-butenyl.
  • Halogen is fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.
  • a divalent aliphatic or aromatic radical Yi is, for example, Ci-dsalkylene, linear or branched, uninterrupted or interrupted by one or more O atoms and unsubstituted or substituted by OH; or cycloalkylene, e.g. cyclohexylene, the term cycloalkylene also including radicals such as, for example, -CH 2 -cyclohexylene-CH 2 -.
  • a corresponding aromatic radical is, for example, phenylene, naphthylene, biphenylene, all unsubstituted or substituted, and all optionally additionally substituted at the bonds by alkylene in a manner analogous to that described for cycloalkylene.
  • R ⁇ o as substituted 9H-carbazol-3-yl is preferably substituted by C C ⁇ 2 alkyl, and -(CO)- phenyl or -(CO)-phenylene-C ⁇ -C 4 alkyl, substitution being possible at one of the aromatic rings and at the N atom.
  • R 6 o is in this case especially a radical of formula
  • R 3 ⁇ is hydroxy, Ci-Ciealkoxy, morpholino or dimethylamino
  • RM, RM and R 36 and R 3 , R 38 and R 39 are hydrogen or d-dalkyl
  • R 40 is Ci-Caalkyl, unsubstituted phenyl, or phenyl substituted by Ci-Caalkyl or/and by
  • R « is (CO)R 2 ;
  • R 2 is phenyl substituted by C ⁇ -C 4 alkyl or/and by C -C 4 alkoxy;
  • R55, R56, R57, RSB and R59 are hydrogen
  • R 54 is the group
  • Y 1 is -CH 2 CH 2 -0-CH 2 CH 2 -: x is 1;
  • RBO is phenyl substituted by SR 6 3 or f
  • R 6 ⁇ is benzoyl; si is hexyl; and Rra is phenyl.
  • Preferred compounds of formulae V, VI, VII, VIII, IX, X and XI are ⁇ -hydroxycyclohexyl- phenyl-ketone or 2-hydroxy-2-methyl-1-phenyl-propanone, (4-methylthiobenzoyl)-1-methyI- 1-morpholino-ethane, (4-morpholino-benzoyl)-1-benzyl-1-dimethylamino-propane, (4-morph- olino-benzoyl)-1-(4-methylbenzyl)-1-dimethylamino-propane, (3,4-dimethoxy-benzoyl)-1- benzyl-1-dimethylamino-propane, be ⁇ zil dimethyl ketal, (2,4,6-trimethylbenzoyl)-diphe ⁇ yl- phosphine oxide, bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethyl-pent-1-yl)phosphine oxide,
  • R 32 and R 33 are each independently of the other C ⁇ -C 6 alkyl or, together with the carbon atom to which they are bonded, form a cyclohexyl ring and R 31 is hydroxy.
  • R ⁇ is phenyl unsubstituted or substituted by from one to three C ⁇ -C ⁇ 2 alkyl or/and
  • Rn Is the group (CO)R 2 or phenyl
  • R 42 is phenyl substituted by from one to three C ⁇ -C 4 alkyl or Ci-dalkoxy substituents.
  • the preparation of the compounds of formulae V, VI, VII, VIII, IX, X and XI is generally known to the person skilled in the art and some of the compounds are commercially available.
  • the preparation of oligomeric compounds of formula V is described, for example, in EP 161 463.
  • a description of the preparation of compounds of formula VI can be found, for example, in EP 209831.
  • the preparation of compounds of formula VII is disclosed, for example, in EP 7508, EP 184 095 and GB 2 259 704.
  • the preparation of compounds of formula VIII is described, for example, in EP 318 894, EP 318 893 and EP 565488.
  • the electrical energy can be coupled in by inductive or capacitive means. It may be direct current or alternating current; the frequency of the alternating current may range from a few kHz up into the MHz range. A power supply in the microwave range (GHz) is also possible.
  • GHz microwave range
  • primary plasma gases it is possible to use, for example, He, argon, xenon, N 2 , 0 2 , H 2 , steam or air, and also mixtures of those compounds.
  • the process according to the invention is not sensitive per se in respect of the coupling-in of the electrical energy.
  • the process can be carried out batchwise, for example in a rotating drum, or continuously in the case of films, fibres or woven fabrics. Such methods are known and are described in the prior art.
  • the process can also be carried out under corona discharge conditions.
  • Corona discharges are produced under normal pressure conditions, the ionised gas most frequently used being air.
  • other gases and mixtures are also possible, as described, for example, in COATING Vol. 2001, No. 12, 426, (2001).
  • air as ionisation gas in corona discharges is that the operation can be carried out in an apparatus open to the outside and, for example, a film can be drawn through continuously between the discharge electrodes.
  • Such process arrangements are known and are described, for example, in J. Adhesion Sci. Technol. Vol 7, No. 10, 1105, (1993).
  • Three-dimensional workpieces can be treated with a free plasma jet, the contours being followed with the assistance of robots.
  • the flame treatment of substrates is known to the person skilled in the art.
  • Corresponding industrial apparatus for example for the flame treatment of films, is commercially available.
  • a film is conveyed on a cooled cylindrical roller past the flame- treatment apparatus, which consists of a chain of burners arranged in parallel, usually along the entire length of the cylindrical roller. Details can be found in the brochures of the manufacturers of flame-treatment apparatus (e.g. esse Cl, flame treaters, Italy).
  • the parameters to be chosen are governed by the particular substrate to be treated. For example, the flame temperatures, the flame intensity, the dwell times, the distance between substrate and burner, the nature of the combustion gas, air pressure, humidity, are matched to the substrate in question.
  • As flame gases it is possible to use, for example, methane, propane, butane or a mixture of 70 % butane and 30 % propane.
  • the inorganic or organic substrate to be treated can be in any solid form.
  • the substrate is preferably in the form of a woven fabric, a fibre, a film or a three-dimensional workpiece.
  • the substrate may be, for example, a thermoplastic, elastomeric, inherently crosslinked or crosslinked polymer, a metal oxide, a ceramic material, glass, metal, leather or textile.
  • the pretreatment of the substrate in the form of plasma-, corona- or flame-treatment can be carried out, for example, immediately after the extrusion of a fibre or film, and also directly after film-drawing.
  • the inorganic or organic substrate is preferably a thermoplastic, elastomeric, inherently crosslinked or crosslinked polymer, a metal oxide, a ceramic material, a glass or a metal, especially a thermoplastic, elastomeric, inherently crosslinked or crosslinked polymer.
  • thermoplastic, elastomeric, inherently crosslinked or crosslinked polymers examples include thermoplastic, elastomeric, inherently crosslinked or crosslinked polymers.
  • Polymers of mono- and di-olefins for example polypropylene, polyisobutylene, poly- butene-1 , poly-4-methylpentene-1 , polyisoprene or polybutadiene and also polymerisation products of cyclo-olefins, for example of cyclopentene or norbornene; and also polyethylene (which may optionally be crosslinked), for example high density polyethylene (HDPE), high density polyethylene of high molecular weight (HDPE-HMW), high density polyethylene of ultra-high molecular weight (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), and linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
  • HDPE high density polyethylene
  • HDPE-HMW high density polyethylene of high molecular weight
  • HDPE-UHMW high density polyethylene of ultra-high molecular weight
  • MDPE medium density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear
  • Polyolefins that is to say polymers of mono-olefins, as mentioned by way of example in the preceding paragraph, especially polyethylene and polypropylene, can be prepared by various processes, especially by the following methods: a) by free-radical polymerisation (usually at high pressure and high temperature); b) by means of a catalyst, the catalyst usually containing one or more metals of group IVb, Vb, Vlb or VIII. Those metals generally have one or more ligands, such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls, which may be either ⁇ - or ⁇ -coordinated.
  • ligands such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls, which may be either ⁇ - or ⁇ -coordinated.
  • Such metal complexes may be free or fixed to carriers, for example to activated magnesium chloride, titanium(lll) chloride, aluminium oxide or silicon oxide.
  • Such catalysts may be soluble or insoluble in the polymerisation medium.
  • the catalysts can be active as such in the polymerisation or further activators may be used, for example metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyl oxanes, the metals being elements of group(s) la, Ha and/or Ilia.
  • the activators may have been modified, for example, with further ester, ether, amine or silyl ether groups.
  • Such catalyst systems are usually referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or Single Site Catalysts (SSC)
  • Copolymers of mono- and di-olefins with one another or with other vinyl monomers for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/butene-1 copolymers, propylene/isobutylene copolymers, ethylene/butene-1 copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/- alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and copolymers thereof with carbon monoxide, or ethylene/acrylic acid copolymers and salts thereof (lonomers), and
  • Hydrocarbon resins for example Cs-C 9
  • hydrogenated modifications thereof for example tackifier resins
  • Copolymers of styrene or ⁇ -methylstyrene with dienes or acrylic derivatives for example styrene/butadiene, styrene/acrylonit ⁇ le, styrene/alkyl methacrylate, styrene/buta- diene/alkyl acrylate and methacrylate, styrene/maleic anhydride, styrene/acrylonit ⁇ le/methyl acrylate, high-impact-strength mixtures consisting of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer, and also block copolymers of styrene, for example styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene-butylene
  • Graft copolymers of styrene or ⁇ -methylstyrene for example styrene on polybuta- diene, styrene on polybutadiene/styrene or polybutadiene/acrylonit ⁇ le copolymers, styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleic acid imide on polybutadiene; styrene and maleic acid imide on polybutadiene, styrene and maleic acid imide on polybutadiene, styrene and alkyl acrylates or alkyl methacrylates on polybutadiene, styrene and acryl
  • Halogen-containing polymers for example polychloroprene, chlorinated rubber, chlorinated and brominated copolymer of isobutylene/isoprene (halobutyl rubber), chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and co-polymers, especially polymers of halogen- containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; and copolymers thereof, such as vinyl chloride/- vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate.
  • halogen-containing polymers for example polychloroprene, chlorinated rubber, chlorinated and brominated copolymer of isobutylene/isoprene (halobutyl rubber), chlorinated or chlorosulf
  • Polymers derived from ⁇ , ⁇ -unsaturated acids and derivatives thereof such as poly- acrylates and polymethacrylates, or polymethyl methacrylates, polyacrylamides and poly- acrylonitriles impact-resistant-modified with butyl acrylate.
  • Copolymers of the monomers mentioned under 9) with one another or with other unsaturated monomers for example acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate copolymers, acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
  • Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate or maleate, poly- vinylbutyral, polyallyl phthalate, polyallylmelamine; and the co polymers thereof with olefins mentioned in Point 1.
  • cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
  • Polyacetals such as polyoxymethylene, and also those polyoxymethylenes which contain comonomers, for example ethylene oxide; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
  • Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides derived from m-xylene, diamine and adipic acid; polyamides prepared from hexa- methylenediamine and iso- and/or tere-phthalic acid and optionally an elastomer as modifier, for example poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m- phenylene isophthalamide.
  • Polyureas Polyureas, polyimides, polyamide imides, polyether imides, polyester imides, poly- hydantoins and polybenzimidazoles.
  • Polyesters derived from dicarboxylic acids and dialcohols and/or from hydroxy- carboxylic acids or the corresponding lactones such as polyethylene terephthalate, polybutylene' terephthalate, poly-1 ,4-dimethylolcyclohexane terephthalate, polyhydroxy- benzoates, and also block polyether esters derived from polyethers with hydroxyl terminal groups; and also polyesters modified with polycarbonates or MBS.
  • Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols, and also vinyl compounds as crosslinking agents, and also the halogen-containing, difficultly combustible modifications thereof.
  • Crosslinkable acrylic resins derived from substituted acrylic esters, e.g. from epoxy acrylates, urethane acrylates or polyester acrylates.
  • Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of bisphenol A diglycidyl ethers, bisphenol F diglycidyl ethers, that are crosslinked using customary hardeners, e.g. anhydrides or amines with or without accelerators.
  • Natural polymers such as cellulose, natural rubber, gelatin, or polymer- homologously chemically modified derivatives thereof, such as cellulose acetates, propionates and butyrates, and the cellulose ethers, such as methyl cellulose; and also colophonium resins and derivatives.
  • Mixtures (polyblends) of the afore-mentioned polymers for example PP/EPDM, poly- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA PPO, PBT/PC/ABS or PBT/PET/PC.
  • the substrate can be, for example, a substrate as used in the field of commercial printing, for sheet-fed intaglio printing, sheetfed gravure printing, sheetfed offset printing or endless printing, posters, calendars, forms, labels, packaging films, tapes, credit cards, furniture profiles efc..
  • the substrate is not confined to use in the non-nutrition sector.
  • the substrate may also be, for example, a material for use in the field of nutrition, e.g. as packaging for foodstuffs, cosmetics, medicaments, efc..
  • substrates have been pretreated according to processes of the invention it is also possible, for example, for substrates that usually have poor compatibility with one another to be adhesively bonded to one another or laminated.
  • paper should also be understood as being an inherently crosslinked polymer, especially in the form of card(board), which can additionally be coated with e.g. Teflon®.
  • substrates are, for example, commercially available.
  • the thermoplastic, crosslinked or inherently crosslinked plastics is preferably a polyolefin, polyamide, polyacrylate, polycarbonate, polystyrene or an acrylic/melamine, alkyd or poly- urethane coating.
  • Polycarbonate, polyethylene and polypropylene are especially preferred.
  • the plastics may be, for example, in the form of films, injection-moulded articles, extruded workpieces, fibres, felts or woven fabrics.
  • inorganic substrates there come into consideration especially glass, ceramic materials, metal oxides and metals. They may be silicates and semi-metal or metal oxide glasses which are preferably in the form of layers or in the form of powders preferably having average particle diameters of from 10 nm to 2000 ⁇ m. The particles may be dense or porous. Examples of oxides and silicates are Si0 2 , Ti0 2 , Zr0 2 , MgO, NiO, W0 3 , Al 0 3 , La 2 0 3 , silica gels, clays and zeolites.
  • Preferred inorganic substrates, in addition to metals are silica gels, aluminium oxide, titanium oxide and glass and mixtures thereof.
  • metal substrates there come into consideration especially Fe, Al, Ti, Ni, Mo, Cr and steel alloys.
  • the workpiece can be stored or immediately processed further, there being applied by means of known technology either (preferred) a radiation-curable coating containing ethylenically unsaturated bonds, or a coating that dries/cures in some other way, e.g. a printing ink.
  • a radiation-curable coating containing ethylenically unsaturated bonds or a coating that dries/cures in some other way, e.g. a printing ink.
  • This can be effected by means of pouring, immersion, spraying, coating, knife application, roller application or spin- coating.
  • the unsaturated compounds of the radiation-curable composition in process step d1) may contain one or more ethylenically unsaturated double bonds. They may be lower molecular weight (monomeric) or higher molecular weight (oligomeric). Examples of monomers having a double bond are alkyl and hydroxyalkyl acrylates and methacrylates, e.g. methyl, ethyl, butyl, 2-ethylhexyl and 2-hydroxyethyl acrylate, isobornyl acrylate and methyl and ethyl methacrylate. Also of interest are silicone acrylates.
  • acrylo nitrile acrylamide, methacrylamide, N-substituted (meth)acrylamides
  • vinyl esters such as vinyl acetate, vinyl ethers, such as isobutyl vinyl ether, styrene, alkyl- and halo-styrenes, N- vinylpyrrolidone, vinyl chloride and vinylidene chloride.
  • Examples of monomers having more than one double bond are ethylene glycol diacrylate, 1 ,6-hexanediol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, hexamethylene glycol diacrylate and bisphenol A diacrylate, 4,4'-bis(2-acryloyloxyethoxy)diphenylpropane, trimethylol- propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, vinyl acrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, tris(hydroxyethyl) isocyanurate triacrylate (Sartomer 368; from Cray Valley) and tris(2- acryloylethyl) isocyanurate.
  • acrylic esters of alkoxylated polyols for example glycerol ethoxylate triacrylate, glycerol propoxylate triacrylate, tri methylol- propaneethoxylate triacrylate, trimethylolpropanepropoxylate triacrylate, pentaerythritol ethoxylate tetraacrylate, pentaerythritol propoxylate triacrylate, pentaerythritol propoxylate tetraacrylate, neopentyl glycol ethoxylate diacrylate or neopentyl glycol propoxylate diacrylate.
  • the degree of alkoxylation of the polyols used may vary.
  • oligomeric polyunsaturated compounds examples include acrylated epoxy resins, acrylated or vinyl-ether- or epoxy-group-containing polyesters, polyurethanes and polyethers.
  • unsaturated oligomers are unsaturated polyester resins, which are usually produced from maleic acid, phthalic acid and one or more diols and have molecular weights of about from 500 to 3000.
  • vinyl ether monomers and oligomers and also maleate-terminated oligomers having polyester, polyurethane, polyether, polyvinyl ether and epoxide main chains.
  • esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides and polymers having ethylenically unsaturated groups in the chain or in side groups, e.g. unsaturated polyesters, polyamides and polyurethanes and copoly- mers thereof, alkyd resins, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers having (meth)acrylic groups in side chains, and also mixtures of one or more such polymers.
  • esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides and polymers having ethylenically unsaturated groups in the chain or in side groups, e.g. unsaturated polyesters, polyamides and polyurethanes and copoly- mers thereof, alkyd resins, polybutadiene and butadiene copolymers,
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid and unsaturated fatty acids such as linolenic acid or oleic acid.
  • Acrylic and methacrylic acid are preferred.
  • Suitable polyols are aromatic and especially aliphatic and cycloaliphatic polyols.
  • aromatic polyols are hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-di(4-hydroxyphenyl)pro- pane, and novolaks and resols.
  • polyepoxides are those based on the said polyols, especially the aromatic polyols and epichlorohydrin.
  • Also suitable as polyols are polymers and copolymers that contain hydroxyl groups in the polymer chain or in side groups, e.g. polyvinyl alcohol and copolymers thereof or polymethacrylic acid hydroxyalkyl esters or copolymers thereof.
  • Further suitable polyols are oligoesters having hydroxyl terminal groups.
  • aliphatic and cycloaliphatic polyols include alkylenediols having preferably from 2 to 12 carbon atoms, such as ethylene glycol, 1 ,2- or 1 ,3-propanediol, 1,2-, 1,3- or 1 ,4- butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycols having molecular weights of preferably from 200 to 1500, 1 ,3- cyclopentanediol, 1 ,2-, 1,3- or 1 ,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol, tris( ⁇ -hydroxyethyl)amine, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaeryth
  • the polyols may have been partially or fully esterified by one or by different unsaturated carboxylic acid(s), it being possible for the free hydroxyl groups in partial esters to have been modified, for example etherified, or esterified by other carboxylic acids.
  • esters are: trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacryl- ate, 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, dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaeryth
  • polyamines are ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-, 1,3- or 1 ,4-butylenediamine, 1,5-pentylenediami ⁇ e, 1,6- hexylenediamine, octylenediamine, dodecylenediamine, 1,4-diamino-cyclohexane, isophor- onediamine, phenylenediamine, bisphenylenediamine, di- ⁇ -aminoethyl ether, diethylenetri- amine, triethylenetetramine and di( ⁇ -aminoethoxy)- and di( ⁇ -aminopropoxy)-ethane.
  • polyamines are polymers and copolymers which may have additional amino groups in the side chain and oligoamides having amino terminal groups.
  • unsaturated amides are: methylene bisacrylamide, 1,6-hexamethylene bisacrylamide, diethylenetriamine trismethacrylamide, bis(methacrylamidopropoxy)ethane, ⁇ -methacryl- amidoethyl methacrylate and N-[( ⁇ -hydroxyethoxy)ethyl]-acrylamide.
  • Suitable unsaturated polyesters and polyamides are derived, for example, from maleic acid and diols or diamines.
  • the maleic acid may have been partially replaced by other dicarboxylic acids. They may be used together with ethylenically unsaturated comonomers, e.g. styrene.
  • the polyesters and polyamides may also be derived from dicarboxylic acids and ethylenically unsaturated diols or diamines, especially from those having longer chains of e.g. from 6 to 20 carbon atoms.
  • Examples of polyurethanes are those composed of saturated diisocyanates and unsaturated diols or unsaturated diisocyanates and saturated diols.
  • Suitable comonomers include, for example, olefins, such as ethylene, propene, butene, hexene, (meth)acrylates, acrylonitrile, styrene and vinyl chloride. Polymers having (meth)acrylate groups in the side chain are likewise known.
  • Examples are reaction products of novolak-based epoxy resins with (meth)acrylic acid; homo- or co-polymers of vinyl alcohol or hydroxyalkyl derivatives thereof that have been esterified with (meth)acrylic acid; and homo- and co-polymers of (meth)acrylates that have been esterified with hydroxyalkyl (meth)acrylates.
  • acrylates that have been modified by the reaction with primary or secondary amines, as described e.g. in US 3844 916, in EP 280 222, in US 5482 649 or in US 5 734 002.
  • Such amine-modified acrylates are also termed aminoacrylates.
  • Amino- acrylates are obtainable e.g.
  • RTM EBECRYL 80 under the name RTM EBECRYL 80, RTM EBECRYL 81, RTM EBECRYL 83, RTM EBECRYL 7100 from UCB Chemicals
  • RTMLaromer PO 83F under the name RTM Laromer PO 84F, R TMLaromer PO 94F from BASF
  • RTM PHOTOMER 4775 F T PHOTOMER 4967 F from Cognis
  • RTM CN501 under the name RTM CN501, R TMCN503, RTM CN550 from Cray Valley.
  • (meth)acrylate includes both the acrylate and the methacrylate.
  • An acrylate or methacrylate compound is especially used as the mono- or poly-ethylenically unsaturated compound.
  • composition in step d1) in addition to comprising at least one ethylenically unsaturated monomer or oligomer, preferably comprises at least one further photoinitiator or coinitiator for the curing with UV ⁇ /IS radiation.
  • the invention therefore relates also to a process wherein in process step d1) a photo- polymerisable composition, comprising at least one ethylenically unsaturated monomer or/and oligomer and at least one photoinitiator and/or coinitiator, is applied to the pretreated substrate and cured by means of UV ⁇ /IS radiation.
  • UV ⁇ /IS radiation is to be understood as being electromagnetic radiation in a wavelength range from 150 nm to 700 nm. Preference is given to the range from 250 nm to 500 nm. Suitable lamps are known to the person skilled in the art and are commercially available.
  • the photosensitivity of the compositions according to process step d1) usually extends from approximately 150 nm to approximately 600 nm (UV field).
  • a large number of the most varied kinds of light source may be used.
  • Both point sources and planiform radiators (lamp arrays) are suitable. Examples are: carbon arc lamps, xenon arc lamps, medium-pressure, super-high-pressure, high-pressure and low-pressure mercury radiators doped, where appropriate, with metal halides (metal halide lamps), microwave-excited metal vapour lamps, excimer lamps, superactinic fluorescent tubes, fluorescent lamps, argon incandescent lamps, flash lamps, photographic floodlight lamps, light-emitting diodes (LED), electron beams and X-rays.
  • metal halides metal halide lamps
  • microwave-excited metal vapour lamps excimer lamps
  • superactinic fluorescent tubes fluorescent lamps
  • fluorescent lamps argon incandescent lamps
  • flash lamps photographic floodlight lamps
  • the distance between the lamp and the substrate to be irradiated may vary according to the intended use and the type and strength of the lamp and may be, for example, from 2 cm to 150 cm. Also suitable are laser light sources, for example excimer lasers, such as Krypton-F lasers for irradiation at 248 nm. Lasers in the visible range may also be used. This method may be used to produce printed circuits in the electronics industry, lithographic offset printing plates or relief printing plates and also photographic image-recording materials.
  • the curing of the composition applied in process step d1) or d2) may, in addition, likewise be carried out with daylight or with light sources equivalent to daylight.
  • the dose of radiation used in process step c) is e.g. from 1 to 1000 mJ/cm 2 , such as 1-800 mJ/cm 2 , or, for example, 1-500 mJ/cm 2 , e.g. from 5 to 300 mJ/cm 2 , preferably from 10 to 200 mJ/cm 2 .
  • photoinitiator in the radiation-curable compositions according to process step d1) it is possible to use compounds of formula I, II, III or IV or any initiators and initiator systems known from the prior art.
  • photoinitiators without unsaturated groups.
  • Typical examples are mentioned below, which can be used either singly or in admixture with one another.
  • photoinitiators are the compounds of formulae V, VI, VII, VIII, IX, X and XI described hereinbelore.
  • sensitisers which shift or broaden the spectral sensitivity and thus bring about an acceleration of the photopolymerisation.
  • They are especially aromatic carbonyl compounds, for example benzophenone, thioxanthone, especially isopropyl thioxanthone, anthraquinone and 3- acylcoumarin derivatives, terphenyls, styryl ketones, and also 3-(aroylmethylene)- thiazolines, camphor quinone, and also eosine, rhodamine and erythrosine dyes.
  • Amines for example, can also come into consideration as photosensitisers when the photoinitiator layer grafted on according to the invention consists of a benzophenone or benzophenone derivative. Further examples of photosensitisers are 1. Thioxanthones
  • Benzophenone 4-phenylbenzophenone, 4-methoxybenzophenone, 4,4'-dimethoxybenzo- phenone, 4,4'-dimethylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dimethylamino- benzophenone, 4,4'-diethylaminobenzophenone, 4-methylbenzophenone, 3-methyl-4'- phenylbenzophenone, 2,4,6-trimethylbenzophenone, 2,4,6-trimethyl-4'-phenyl-benzo- phenone, 4-(4-methylthiophenyl)-benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, methyl 2-benzoylbenzoate, 4-(2-hydroxyethylthio)-benzophenone, 4-(4-tolylthio)benzo- phenone, 4-benzoyl-N,N,N-trimethylbenzenemethanaminium chloride, 2-hydroxy-3-
  • the radiation-curable composition may comprise further additives, especially light stabilisers.
  • additional additives especially light stabilisers.
  • the nature and amount of such additional additives is governed by the intended use of the coating in question and will be familiar to the person skilled in the art.
  • compositions may also be pigmented when a suitable photoinitiator is chosen, it being possible for coloured pigments as well as white pigments to be used.
  • compositions can be applied in layer thicknesses of from about 0.1 ⁇ m to about 1000 ⁇ m, especially about from 1 ⁇ m to 100 ⁇ m.
  • pigmented compositions e.g. are also referred to as printing inks.
  • UV absorbers e.g. those of the hydroxyphenyl- benzotriazole, hydroxyphenylbenzophenone, oxalic acid amide or hydroxyphenyl-s-triazine type.
  • UV absorbers e.g. those of the hydroxyphenyl- benzotriazole, hydroxyphenylbenzophenone, oxalic acid amide or hydroxyphenyl-s-triazine type.
  • HALS sterically hindered amines
  • 2-(2'-Hvdroxyphenyl)-benzotriazoles e.g. 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, 2- (3',5'-di-tert-butyl-2'-hydroxyphenyl)-benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl)-benzo- triazole, 2-(2'-hydroxy-5'-(1,1 ,3,3-tetramethylbutyl)-phenyl)-benzotriazole, 2-(3',5'-di-tert- butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5- chlorobenzotriazole, 2-(3'-sec-butyl-5 , -tert-butyl-2'-hydroxyphenyl)-benzotriazole, 2-(2'-hyl
  • 2-Hvdroxybenzophenones e.g. the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4- dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy or 2'-hydroxy-4,4'-dimethoxy derivative.
  • Esters of unsubstituted or substituted benzoic acids e.g. 4-tert-butyl- ⁇ henyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)- resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, 3,5-di-tert-butyl-4-hydroxy- benzoic acid octadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2-methyl-4,6-di-tert- butylphenyl ester.
  • Acrylates e.g. ⁇ -cyano- ⁇ , ⁇ -diphenylacrylic acid ethyl ester or isooctyl ester, ⁇ -methoxy- carbonylcinnamic acid methyl ester, ⁇ -cyano- ⁇ -methyl-p-methoxycinnamic acid methyl ester or butyl ester, ⁇ -methoxycarbonyl-p-methoxycinnamic acid methyl ester, N-( ⁇ -methoxy- carbo ⁇ yl- ⁇ -cyanovinyl)-2-methyl-indoline.
  • Stericallv hindered amines e.g. bis(2,2,6,6-tetramethylpiperidyl) sebacate, bis(2, 2,6,6- tetramethylpiperidyl) succinate, bis(1, 2,2,6, 6-pentamethylpiperidyl) sebacate, n-butyl-3,5-di- tert-butyl-4-hydroxybenzylmalonic acid bis(1 ,2,2,6,6-pentamethylpiperidyl) ester, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1 ,3,5-s-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotri- acetate
  • Oxalic acid diamides e.g. 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy- 5,5'-di-tert-butyl oxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyl oxanilide, 2-ethoxy-2'-ethyl oxanilide, N,N'-bis(3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyl oxanilide and a mixture thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyl oxanilide, mixtures of o- and p- methoxy- and also of o- and p-ethoxy-di-substituted oxan
  • Phosphites and phosphonites e.g. triphenyl phosphite, diphenylalkyl phosphites, phenyl- dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl-pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecylpenta- erythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert- butyl-4-methylphenyl)pentaerythritol diphosphite, bis-isodecyloxy-pentaerythritol diphos
  • additives customary in the art e.g. antistatics, flow improvers and adhesion promoters.
  • Compositions applied in process step d1) or d2) are, for example, pigmented or unpigmented surface coatings, inks, ink-jet inks; printing inks, for example screen printing inks, offset printing inks, flexographic printing inks; or overprint varnishes; or primers; or printing plates, offset printing plates; powder coatings, adhesives, pressure -sensitive adhesives, e.g. including hot-melt pressure-sensitive adhesives, or repair coatings, repair varnishes or repair putty compositions.
  • compositions used in process step d1) need not necessarily comprise a photoinitiator — for example they may be customary electron-beam-curable compositions (without photoinitiator) known to the person skilled in the art.
  • the substrates pretreated using steps a) - c) in accordance with the process of the invention can, as already mentioned, be coated in a further step d1) with customary photocurable compositions and cured with UV ⁇ IS or an electron beam or d2) can be provided with a customary coating, such coatings being dried, for example, in air or thermally.
  • the drying can be effected, for example, also by absorption, for example by penetration into the substrate.
  • the coating used in process step d2) is preferably a printing ink.
  • They are, for example, pigmented printing inks and printing inks coloured with dyes.
  • a printing ink is, for example, a liquid or paste-form dispersion that comprises colorants
  • binders and also optionally solvents and/or optionally water and additives.
  • the binder and, if applicable, the additives are generally dissolved in a solvent.
  • Customary viscosities in the Brookfield viscometer are, for example, from 20 to 5000 mPa-s, for example from 20 to 1000 Pa ⁇ s, for liquid printing inks.
  • the values range, for example, from 1 to 100 Pa-s, preferably from 5 to 50 Pa'S.
  • the person skilled in the art will be familiar with the ingredients and compositions of printing inks.
  • Suitable pigments like the printing ink formulations customary in the art, are generally known and widely described.
  • Printing inks comprise pigments advantageously in a concentration of, for example, from 0.01 to 40 % by weight, preferably from 1 to 25 % by weight, especially from 5 to 10 % by weight, based on the total weight of the printing ink.
  • the printing inks can be used, for example, for intaglio printing, flexographic printing, screen printing, offset printing, lithography or continuous or dropwise ink-jet printing on material pretreated in accordance with the process of the invention using generally known formulations, for example in publishing, packaging or shipping, in logistics, in advertising, in security printing or in the field of office equipment.
  • Suitable printing inks are both solvent-based printing inks and water-based printing inks. Of interest are, for example, printing inks based on aqueous acrylate. Such inks are to be understood as including polymers or copolymers that are obtained by polymerisation of at ff H *,? fi 0 / least one monomer containing a group — c-c-o— or — C-C-N- and that are dissolved in water or a water-containing organic solvent.
  • Suitable organic solvents are water-miscible solvents customarily used by the person skilled in the art, for example alcohols, such as methanol, ethanol and isomers of propanol, butanol and pentanol, ethylene glycol and ethers thereof, such as ethylene glycol methyl ether and ethylene glycol ethyl ether, and ketones, such as acetone, ethyl methyl ketone or cyclo, for example isopropanol. Water and alcohols are preferred.
  • Suitable printing inks comprise, for example, as binder primarily an acrylate polymer or copolymer and the solvent is selected, for example, from the group consisting of water,
  • Ci-Csalcohols ethylene glycol, 2-(d-C 5 alkoxy)-ethanoI, acetone, ethyl methyl ketone and any mixtures thereof.
  • the printing inks may also comprise customary additives known to the person skilled in the art in customary concentrations.
  • a printing ink is usually prepared by dilution of a printing ink concentrate and can then be used in accordance with methods known perse.
  • the printing inks may, for example, also comprise alkyd systems that dry oxidatively.
  • the printing inks are dried in a known manner customary in the art, optionally with heating of the coating.
  • a suitable aqueous printing ink composition comprises, for example, a pigment or a combination of pigments, a dispersant and a binder.
  • Dispersants that come into consideration include, for example, customary dispersants, such as water-soluble dispersants based on one or more arylsulfonic acid/formaldehyde condensation products or on one or more water-soluble oxalkylated phenols, non-ionic dispersants or polymeric acids.
  • customary dispersants such as water-soluble dispersants based on one or more arylsulfonic acid/formaldehyde condensation products or on one or more water-soluble oxalkylated phenols, non-ionic dispersants or polymeric acids.
  • arylsulfonic acid/formaldehyde condensation products are obtainable, for example, by sulfonation of aromatic compounds, such as naphthalene itself or naphthalene-containing mixtures, and subsequent condensation of the resulting arylsulfonic acids with formaldehyde.
  • aromatic compounds such as naphthalene itself or naphthalene-containing mixtures
  • condensation of the resulting arylsulfonic acids with formaldehyde Such dispersants are known and are described, for example, in US-A- 5 186 846 und DE-A-19727 767.
  • Suitable oxalkylated phenols are likewise known and are described, for example, in US-A-4218 218 und DE-A-197 27 767.
  • Suitable non-ionic dispersants are, for example, alkylene oxide adducts, polymerisation products of vinylpyrrolidone, vinyl acetate or vinyl alcohol and co- or ter-polymers of vinyl pyrrolidone with vinyl acetate and/or vinyl alcohol.
  • suitable binder components include acrylate-group- containing, vinyl-group-containing and/or epoxy-group-containing monomers, prepolymers and polymers and mixtures thereof. Further examples are melamine acrylates and silicone acrylates.
  • the acrylate compounds may also be non-ionically modified (e.g. provided with amino groups) or ionically modified (e.g. provided with acid groups or ammonium groups) and used in the form of aqueous dispersions or emulsions (e.g. EP-A-704 469, EP-A-12 339).
  • the solventless acrylate polymers can be mixed with so-called reactive diluents, for example vinyl- group-containing monomers.
  • Further suitable binder components are epoxy-group- containing compounds.
  • the printing ink compositions may also comprise as additional component, for example, an agent having a water-retaining action (humectant), e.g. polyhydric alcohols, polyalkylene glycols, which renders the compositions especially suitable for ink-jet printing.
  • an agent having a water-retaining action e.g. polyhydric alcohols, polyalkylene glycols, which renders the compositions especially suitable for ink-jet printing.
  • the printing inks may comprise further auxiliaries, such as are customary especially for (aqueous) ink-jet inks and in the printing and coating industries, for example preservatives (such as glutardialdehyde and/or tetramethylolacetyleneurea, anti- oxidants, degassers/defoamers, viscosity regulators, flow improvers, anti-settling agents, gloss improvers, lubricants, adhesion promoters, anti-skin agents, matting agents, emulsifiers, stabilisers, hydrophobic agents, light stabilisers, handle improvers and antistatics.
  • preservatives such as glutardialdehyde and/or tetramethylolacetyleneurea, anti- oxidants, degassers/defoamers, viscosity regulators, flow improvers, anti-settling agents, gloss improvers, lubricants, adhesion promoters, anti-skin agents, matting agents,
  • Printing inks suitable in process step d2) also include, for example, those comprising a dye (with a total content of dyes of e.g. from 1 to 35 % by weight, based on the total weight of the ink).
  • Such printing inks may comprise organic solvents, e.g. water-miscible organic solvents, for example C ⁇ -C 4 alcohols, amides, ketones or ketone alcohols, ethers, nitrogen-containing heterocyclic compounds, polyalkylene glycols, C 2 -C e alkylene glycols and thioglycols, further polyols, e.g.
  • glycerol and d-dalkyl ethers of polyhydric alcohols usually in an amount of from 2 to 30 % by weight, based on the total weight of the printing ink.
  • the printing inks may also, for example, comprise solubilisers, e.g. ⁇ -caprolactam.
  • the printing inks may, inter alia for the purpose of adjusting the viscosity, comprise thickeners of natural or synthetic origin. Examples of thickeners include commercially available alginate thickeners, starch ethers or locust bean flour ethers.
  • the printing inks comprise such thickeners e.g. in an amount of from 0.01 to 2 % by weight, based on the total weight of the printing ink.
  • the printing inks may comprise buffer substances, for example borax, borate, phosphate, polyphosphate or citrate, in amounts of e.g. from 0.1 to 3 % by weight, in order to establish a pH value of e.g. from 4 to 9, especially from 5 to 8.5.
  • such printing inks may comprise surfactants or humectants.
  • Surfactants that come into consideration include commercially available anionic and non- ionic surfactants.
  • Humectants that come into consideration include, for example, urea or a mixture of sodium lactate (advantageously in the form of a 50 to 60 % aqueous solution) and glycerol and/or propylene glycol in amounts of e.g. from 0.1 to 30 % by weight, especially from 2 to 30 % by weight, in the printing inks.
  • the printing inks may also comprise customary additives, for example foam- reducing agents or especially substances that inhibit the growth of fungi and/or bacteria.
  • additives are usually used in amounts of from 0.01 to 1 % by weight, based on the total weight of the printing ink.
  • the printing inks may also be prepared in customary manner by mixing the individual components together, for example in the desired amount of water.
  • the viscosity or other physical properties of the printing ink especially those properties which influence the affinity of the printing ink for the substrate in question, to be adapted accordingly.
  • the printing inks are also suitable, for example, for use in recording systems of the kind in which a printing ink is expressed from a small opening in the form of droplets which are directed towards a substrate on which an image is formed.
  • Suitable substrates are, for example, textile fibre materials, paper, plastics or aluminium foils pretreated by the process according to the invention.
  • Suitable recording systems are e.g. commercially available ink- jet printers. Preference is given to printing processes in which aqueous printing inks are used.
  • a metal, semi-metal, metal oxide or semi-metal oxide layer is applied as the strongly adhering layer
  • the following metals are preferred: gold, silver, platinum, palladium, chromium, molybdenum, tin, aluminium or copper, especially aluminium and copper.
  • the following semi-metal and metal oxides are of interest: aluminium oxide, chromium oxide, iron oxide, copper oxide and silicon oxide.
  • the metals, semi-metal or metal oxides are vaporised under vacuum conditions and deposited onto the substrate precoated with photoinitiator.
  • the crucible temperatures for the vaporisation process depend upon the metal or oxide being vaporised and are, for example, 300-2000°C, especially 800-1800°C.
  • the metal-coated substrates are suitable, for example, for flexible circuit board applications, diffusion barrier layers, electromagnetic shields or they form decorative elements.
  • the process according to the invention can be carried out within a wide pressure range, the discharge characteristics shifting as the pressure increases from a pure low-temperature plasma towards a corona discharge and finally changing into a pure corona discharge at an atmospheric pressure of about 1000-1100 mbar.
  • the process is preferably carried out at a process pressure of from 10 " ⁇ mbar up to atmospheric pressure (1013 mbar), especially in the range of from 10 "4 to 10 "2 mbar as a plasma process and at atmospheric pressure as a corona process.
  • the flame treatment is usually carried out at atmospheric pressure.
  • the process is preferably carried out using as the plasma gas an inert gas or a mixture of an inert gas with a reactive gas.
  • air, C0 2 and/or nitrogen are preferably used as the gas. It is especially preferred to use air, H 2 , C0 2 , He, Ar, Kr, Xe, N 2 , 0 2 or H 2 0 singly or in the form of a mixture.
  • the photoinitiator layer deposited preferably has a thickness ranging from e.g. a mono- molecular layer up to 500 nm, especially from 5 nm to 200 nm.
  • the plasma- or corona-treatment of the inorganic or organic substrate a) preferably takes place for from 1 ms to 300 s, especially from 10 ms to 200 s.
  • reaction step b) it is advantageous to apply the photoinitiator as quickly as possible after the plasma-, corona- or flame-pretreatment, but for many purposes it may also be acceptable to carry out reaction step b) after a time delay. It is preferable, however, to carry out process step b) immediately after process step a) or within 24 hours after process step a). Of interest is a process wherein process step c) is carried out immediately after process step b) or within 24 hours after process step b).
  • the pretreated and photoinitiator-coated substrate can be subjected to process step d) [that is to say d1 ) or d2)] immediately after the coating and drying in accordance with process steps a), b) and c) or it can be stored in the pretreated form.
  • the photoinitiator of formula I, II, HI or IV, or where applicable the mixture of a plurality of photoinitiators and/or coinitiators, is applied to the corona-, plasma- or flame-pretreated substrate, for example, in pure form, that is to say without further additives, or in combination with a monomer or oligomer, or dissolved in a solvent.
  • the initiator, or the initiator mixture can also e.g.
  • the initiator can also, for example, be dispersed, suspended or emulsified in water, a dispersant being added as necessary.
  • a dispersant being added as necessary.
  • Suitable dispersants e.g. any surface-active compounds, preferably anionic and non-ionic surfactants, and also polymeric dispersants, are usually known to the person skilled in the art and are described, for example, in US 4965 294 and US 5 168 087.
  • Suitable solvents are in principle any substances in which the photoinitiator, or the photoinitiators, can be converted into a state suitable for application, whether in the form of a solution or in the form of a suspension or emulsion.
  • Suitable solvents are, for example, alcohols, such as ethanol, propanol, isopropanol, butanol, ethylene glycol efc., ketones, such as acetone, methyl ethyl ketone, acetonitrile, aromatic hydrocarbons, such as toluene and xylene, esters and aldehydes, such as ethyl acetate, ethyl formate, aliphatic hydrocarbons, e.g.
  • Suitable monomers and oligomers are, for example, those described above in connection with the photocurable composition (process step d1).
  • the invention therefore relates also to a process wherein the photoinitiators of formula I, II, III and/or IV or mixtures thereof with monomers or oligomers are used in combination with one or more liquids (such as solvents or water) in the form of solutions, suspensions and emulsions.
  • liquids such as solvents or water
  • process step b) Also of interest is a process wherein the photoinitiator used in process step b) or the mixture of photoinitiators is used in molten form.
  • the pretreated substrate for example, 0.1-15 %, e.g. 0.1-5 %, of a photoinitiator of formula I, II, III and/or IV having an unsaturated group and e.g. 0.5-10 % of a monomer, such as an acrylate, methacrylate, vinyl ether efc..
  • the application of the photoinitiators, or mixtures thereof with one another or with monomers or oligomers, in the form of melts, solutions, dispersions, suspensions or emulsions, can be carried out in various ways. Application can be effected by immersion, spraying, coating, brush application, knife application, roller application, printing, spin- coating and pouring. In the case of mixtures of photoinitiators with one another and with coinitiators and sensitisers, all possible mixing ratios can be used. When only one photoinitiator or photoinitiator mixture is to be applied to the pretreated substrate, the concentration of those initiators is, of course, 100 %.
  • the photoinitiators When the photoinitiators are applied in the form of mixtures with monomers or/and solvents or/and water in the form of liquids, solutions, emulsions or suspensions, they are used, for example, in concentrations of from 0.01 to 99.9 %, or 0.01-80 %, e.g. 0.1-50 %, or 10-90 %, based on the solution being applied.
  • the liquids comprising the photoinitiator may, in addition, contain e.g. further substances, such as defoamers, emulsifiers, surfactants, anti- fouling agents, wetting agents and other additives customarily used in the industry, especially the coating and paint industries.
  • drying coatings are known and they can all be used in the claimed process.
  • the irradiation of the coating in order to fix the photoinitiator in process step c) (and also to cure the formulation in process step d1) can be carried out, as already mentioned above, using any sources that emit electromagnetic waves of wavelengths that can be absorbed by the photoinitiators used.
  • sources are generally light sources that emit light in the range from 200 nm to 700 nm. It may also be possible to use electron beams. In addition to customary radiators and lamps it is also possible to use lasers and LEDs (Light Emitting Diodes).
  • the whole area of the coating or parts thereof may be irradiated. Partial irradiation is of advantage when only certain regions are to be rendered adherent. Irradiation can also be carried out using electron beams.
  • the drying and/or irradiation can be carried out under air or under inert gas.
  • Nitrogen gas comes into consideration as inert gas, but other inert gases, such as C0 2 or argon, helium efc. or mixtures thereof, can also be used. Suitable systems and apparatus are known to the person skilled in the art and are commercially available.
  • the invention relates also to the use of photoinitiators of formulae I, II, III and IV and photoinitiator systems comprising at least one compound of formula I, II, III or IV in combination with a further photoinitiator, e.g. a photoinitiator of formula V, VI, VII, VIII, IX, X and/or XI, in the process according to the invention.
  • a further photoinitiator e.g. a photoinitiator of formula V, VI, VII, VIII, IX, X and/or XI
  • the invention relates also to strongly adherent coatings obtainable in accordance with the process described above.
  • Such strongly adherent coatings are important not only as protective layers or coverings, which may additionally be pigmented, but also for image-forming coatings, for example in resist and printing plate technology.
  • image-forming coatings for example in resist and printing plate technology.
  • the irradiation can be effected through a mask or by writing using moving laser beams (Laser Direct
  • Imaging - LDI Such partial irradiation can be followed by a development or washing step in which portions of the applied coating are removed by means of solvents and/or water or mechanically.
  • the image-forming step can be carried out either in process step c) or in process step d).
  • the image-forming step may be a crosslinking reaction or alternatively a reaction in which the solubility of the formulation is altered.
  • the invention therefore relates also to a process wherein portions of the photoinitiators, or mixtures thereof with monomers and/or oligomers, applied in process step b) that have not been crosslinked after irradiation in process step c) are removed by treatment with a solvent and/or water and/or mechanically, and to a process wherein after irradiation in process step d1) portions of the coating are removed by treatment with a solvent and/or water and/or mechanically.
  • the process according to the invention proves to be especially advantageous in respect of improving the adhesion of UV-curing coatings, printing inks, adhesives, on plastics, especially in respect of the adhesion of pigmented coatings. It is possible, for example, to produce pigmented and thick strongly adherent coating layers, for example also with black printing inks which exhibit high absorption.
  • the process according to the invention can be used to improve the adhesion of structurable metal coatings on organic and inorganic substrates.
  • Example 2 the compound according to Example 1 being reacted with the respective starting material indicated in the following Table.
  • the compounds and their physical data are shown in the following Table 1.
  • Example 8 Preparation of 2,4,6-trimethylbenzoyl-isobutyl-allyl- ⁇ hosphine oxide
  • Example 9 The compound of Example 9 is obtained analogously to the method described in Example 8 using the compound described in Example 7 and ally] bromide as starting materials.
  • 31 P-NMR 39.06 ppm; 1 H-NMR (measured irt CDCI 3 ; ppm): 0.90 d; 1.11-1.15 t; 1.20-1.39 m; 1.72-2.14 m; 2.28-2.31 d; 2.76-2.88 m; 5.20-5.27 m; 5.77-5.90 ; 6.86 s.
  • Example 13 Preparation of a mixture of phenyl-(2,4,6-trimethylbenzoyl)-phosphinic acid 2- vinyloxy-ethyl ester and phenyl-(2,4,6-trimethylbenzoyl)-phosphonic acid vinyl ester
  • the crude product is chromato- graphed on silica gel and the product is isolated as a mixture consisting of phenyl-(2,4,6- trimethylbenzoyl)phosphinic acid 2-vinyloxy-ethyl ester and phenyl-(2,4,6-trimethyl- benzoyl)phosphonic acid' vinyl ester in a ratio of 4:1 (according to 1 H-NMR) in the form of a yellowish oil.
  • Examples 14 and 15 are prepared analogously to the method described in Example 10 from 2,4,6-trimethylbenzoic acid chloride and the respective starting material indicated in Table 2.
  • the compounds and the physical data are given in the following Table 3.
  • Example 16 Adhesion of a blue printing ink
  • the thickness is measured by means of a commercially available quartz resonator.
  • a radiation-curable blue printing ink (UV-Temp 43 Y 000 239, Hostmann Steinberg) is applied to the substrates so pretreated in a layer thickness of about 2 ⁇ m. Curing is effected by exposure using a Fusion H lamp (120 W/cm) at a belt speed of 30 m/min. The adhesion properties are tested by crosscutting and tearing off an adhesive tape strip applied to the cured formulation (crosscut test; CC test).
  • Example 17 Adhesion of a blue printing ink
  • Polypropylene films are pretreated as described in Example 16, the photoinitiator according to Example 5 being used. Prior to application of the printing ink, the treated films are stored for 30 days and then coated with printing ink and tested as described in Example 16. Good adhesion is achieved in this case too.
  • Example 18 Adhesion of a blue printing ink
  • Films of polypropylene are subjected to a corona treatment three times at a speed of 20 m/min and an output of 1000 W and then coated with a solution of 1 % of the initiator from Example 3 and 1 % tris(2-hydroxyethyl)-isocyanurate triacrylate in isopropanol using a 6 ⁇ m wire bar. After drying, the films are exposed by means of a Fusion H lamp (120 W/cm) at a belt speed of 15 m/min.
  • PP films (Rayoface Polypropylene Film 58 ⁇ m, UCB) are subjected to a corona treatment at a speed of 50 m/min and an output of 1000 W and then coated with a solution of 1 % of the initiator of Example 3 and 1 % tris(2-hydroxyethyl)-isocyanurate triacrylate in isopropanol by means of a 6 ⁇ m wire bar. After drying, the films are exposed using a Fusion H lamp (120 W/cm) at a belt speed of 15 m/min.
  • a Fusion H lamp 120 W/cm
  • An approximately 1-2 ⁇ m thick layer of a UV- curable blue offset printing ink (Sicura Plast 770, SICPA) is printed onto the resulting treated films by means of an Orange-Proofer (IGT Testing Systems) at a printing force of 500 N.
  • the layer is cured by means of a Fusion H lamp (120 W/cm) at a belt speed of 15 m/min.
  • the evaluation of the crosscut test for the treated films results in a CC value of 0 (no detachment), whereas a solely corona-treated sample has a CC value of 4-5 and an untreated film has a CC value of 5 (complete detachment).

Abstract

In a process for the production of a strongly adherent coating on an inorganic or organic substrate, wherein a), a low-temperature plasma treatment, a corona discharge treatment or a flame treatment is carried out on the inorganic or organic substrate, b) one or more photoinitiators or mixtures of photoinitiators with monomers or/and oligomers, containing at least one ethylenically unsaturated group, or solutions, suspensions or emulsions of the afore-mentioned substances, are applied to the inorganic or organic substrate, and optionally, c) using suitable methods those afore-mentioned substances are dried and/or are irradiated with electromagnetic waves, it proves advantageous to use compounds of formula (I), (II), (III) and/or (IV), IN-L-RG (I), IN-L-RG1-L1-H (II), IN-L-RG1-L1-IN1 (III), IN-L-RG1-L1-RG2-L2-IN1 (IV), wherein IN and IN1 are each independently of the others a monacylphosphine, monoacylphosphine oxide or monoacylphosphine sulfide photoinitiator group; L1 L1 and L2 are a single bond or a spacer group; RG is a monovalent radical having at least one ethylenically unsaturated C=C bond; and RG1 and RG2 are each independently of the other a divalent radical having at least one ethylenically unsaturated C=C bond.

Description

STRONGLYADHERENT SURFACE COATINGS
The invention relates to a process for the production of coatings having good adherence on inorganic or organic substrates, wherein a low-temperature plasma treatment, a corona discharge treatment or a flame treatment is carried out on the inorganic or organic substrate, a specific photoinitiator or a plurality of photoinitiators is applied to the inorganic or organic substrate, and the substrate so precoated with photoinitiator is provided with a further coating. The invention relates also to the use of certain photoinitiators in the production of such layers and to the strongly adherent coatings themselves.
The adhesion properties of coatings (e.g. finishes, paints, printing inks or adhesives) on inorganic or organic substrates, especially on non-polar substrates such as polyethylene, polypropylene or fluorine-containing polyolefins, are frequently inadequate. For that reason additional treatments have to be carried out in order to achieve satisfactory results. The adhesion can be improved by first applying special priming coatings, so-called primers, and only then applying the desired coating thereto.
A further possibility lies in exposing the substrates to be coated to a plasma treatment or corona treatment and then coating them, it being possible for a grafting process with e.g. acrylate monomers to be carried out between those two operations (J. Polym. ScL, Part A: Polym. Chem. 31 , 1307-1314 (1993)).
The production of low-temperature plasmas and the plasma-assisted deposition of thin organic or inorganic layers, both under vacuum conditions and under normal pressure, have been known for some time. Fundamental principles and applications are described, for example, by A. T. Bell, "Fundamentals of Plasma Chemistry" in "Technology and Application of Plasma Chemistry", edited by J. R. Holahan and A. T. Bell, Wiley, New York (1974) and H. Suhr, Plasma Chem. Plasma Process 3(1),1, (1983). Furthermore, in plasmas it is also possible to carry out polymerisations that result in the deposition of polymeric layers and can be used as primers. Fundamental principles and applications are described, for example, by H. Biederman, Y. Osada "Plasma Polymerization Processes" in "Plasma technology 3" edited by L. Holland, Elsevier, Amsterdam 1992.
It is also known that plastics surfaces can be subjected to a plasma treatment and as a result the subsequently applied finish exhibits improved adhesion to the plastics substrate. This is described by H. J. Jacobasch et a/, in Farbe + Lack 99(7), 602-607 (1993) for low- temperature plasmas under vacuum conditions and by J. Friedrich et al. in Surf. Coat. Technol. 59, 371-6(1993) for plasmas ranging from in vacuo up to normal pressure conditions, the low-temperature plasma changing into a corona discharge. A process similar to the kind mentioned at the beginning is known from WO 00/24527. That process describes the plasma treatment of substrates with immediate vapour-deposition and grafting-on of photoinitiators in vacuo for the production of strongly adherent clearcoat layers. Its use is limited to coating using clear, thin varnishes.
WO 01/58971 describes an alternative process in which an electron donor or H donor having an ethylenically unsaturated C=C bond is bonded to a substrate by means of plasma treatment or corona treatment. A strongly adherent coating layer is obtained by adding a suitable coinitiator to the coating being applied.
Some monoacylphosphine oxide (MAPO) photoinitiators having unsaturated C=C double bonds (vinyl benzoyl and vinyl phenyl phosphine) are described by J. H. De Groot et al. in Polym. Mater. Sci. 2001 , (85), 53.
In WO 99/47185, WO 00/55212 and WO 00/55214 the above-described vinyl MAPOs are used for the preparation of UV-crosslinkable copolymers for contact lens manufacture.
There is a need in the art for processes for the pretreatment of substrates that can readily be carried out in practice and are not too complicated in terms of apparatus by means of which the subsequent coating of those substrates is improved.
It has now been found that coatings of photocurable compositions having especially good adherence can be obtained by applying a certain photoinitiator to a substrate to be coated, after that substrate has been subjected to a plasma treatment (low pressure and/or normal pressure plasmas), corona treatment or flame treatment, and drying and/or irradiating the substrate so treated. The substrates so pretreated are provided with a coating and cured. The resulting coatings exhibit surprisingly good adhesion which does not suffer any appreciable deterioration even after several days' storage or exposure to sunlight.
The invention relates to a process for the production of a strongly adherent coating on an inorganic or organic substrate, wherein a) a low-temperature plasma treatment, a corona discharge treatment or a flame treatment is carried out on the inorganic or organic substrate, b) one or more photoinitiators or mixtures of photoinitiators with monomers or/and oligomers, containing at least one ethylenically unsaturated group, or solutions, suspensions or emulsions of the afore-mentioned substances, are applied to the inorganic or organic substrate, and optionally c) using suitable methods those afore-mentioned substances are dried and/or are irradiated with electromagnetic waves, wherein there is used as photoinitiator at least one compound of formula (I), (II), (III) and/or (IV)
IN-L-RG (I)
IN-L-RG1-L1-H (II)
IN-L-RGH-HN! (Ill)
Figure imgf000004_0001
(IV), wherein
IN and IN1 are each independently of the others a monacylphosphine, monoacylphosphine oxide or monoacylphosphine sulfide photoinitiator group;
L, L-i and L2 are each independently of the others a single bond or a spacer group; RG is a monovalent radical having at least one ethylenically unsaturated C=C bond; and RG1 and RG2 are each independently of the other a divalent radical having at least one ethylenically unsaturated C=C bond.
In the process according to the invention it is preferable to use compounds of formulae I and II, especially of formula I.
The monoacylphosphine, monoacylphosphine oxide or monoacylphosphine sulfide photo-
° (E)» initiator group IN or IN1 has, for example, the following structure A-C-P— , wherein
E is O or S; x is O or 1;
A is , cyclopentyl, cyclohexyl, naphthyl, biphenylyl, anthryl or an 0-, S- or N-
Figure imgf000004_0002
containing 5- or 6-membered heterocyclic ring, wherein the radicals cyclopentyl, cyclohexyl, naphthyl, biphenylyl, anthryl or the 0-, S- or N-containing 5- or 6-membered heterocyclic ring are unsubstituted or substituted by halogen, CrC4alkyl or by CrGtalkoxy; Ri and R2 are each independently of the other CrC24alkyl, ORn, CF3 or halogen; R3, 4 and R5 are each independently of the others hydrogen, C1-C24alkyl, OR« or halogen; or two of the radicals Ri, R2, R3, R4 or R5 together are C2-C12alkylene which is uninterrupted or interrupted by one or more O, S or NR 4;
R is Cι-C24alkyl unsubstituted or substituted by C3-C24cycloalkyl, C3-C24cycloalkenyl, phenyl, CN, C(0)Rn, C(0)ORιι, C(0)N(R14)2, OC(0)Rn, 0C(O)0Rn, N(R14)C(0)N(RM), OC(0)NR14, N(R14)C(0)0Rιι, halogen, ORn, SR-n or by N(R12)(R13); or R is C2-C24alkyl interrupted one or more times by non-consecutive O or S and unsubstituted or substituted by phenyl, ORn, CN, C(0)Rn, C(0)ORn or by C(0)N(R14)2; or R is C2-C24alkenyl uninterrupted or interrupted one or more times by non-consecutive O and unsubstituted or substituted by ORn or by Cι-Cι2alkyl; or R is C5-C24cycloalkenyl uninterrupted or interrupted one or more times by non-consecutive O, S or NR14 and unsubstituted or substituted by ORn or by C Cι2alkyl; or R is C -C 4arylalkyl unsubstituted or substituted at the aryl radical by Cι-Cι2alkyl or by Cι-Cι2alkoxy; or R is C4-CZ4cycloalkyl uninterrupted or interrupted one or more times by non-consecutive O, S or NRM and unsubstituted or substituted by OR-π or by d-C12alkyl;
or R is , C8-C24arylcycloalkyl or C8-C24arylcycloalkenyl;
Figure imgf000005_0001
Re, R7, Ra, θ and R10 are each independently of the others hydrogen, CrC24alkyl unsubstituted or substituted by SRn, N(R-|2)(R13), ORn or by phenyl; or Rβ, R7, R8, R9 and R10 are C2-C24alkyl interrupted one or more times by non-consecutive O and unsubstituted or substituted by SRn, N(Rι2)(Rι3), ORn or by phenyl; or R6, R7, R8, R9 and R10 are SRn, (Ri2)(Rι3), ORTJ, phenyl or halogen;
R11 is hydrogen, CrC2oalkyl, C2-C2oalkenyl, C3-C8cycloalkyl, benzyl; or Rn is C2-C2oalkyl interrupted one or more times by O, or C2-C2oalkenyl interrupted one or more times by O; or Rn is phenyl unsubstituted or substituted by CrC4alkyl or by C C alkoxy; R12 and R13 are each independently of the other hydrogen, CrC2oalkyl, C2-C20alkenyl, C3-C8cycloalkyl or benzyl; or Rι2 and R« are C2-C2oalkyl interrupted one or more times by O, or C2-C2oalkenyl interrupted one or more times by O; or R12 and R13 are phenyl unsubstituted or substituted by C C4alkyl or by CrC4alkoxy; or R12 and Rι3, together with the nitrogen atom to which they are bonded, form a 5- or 6-membered ring uninterrupted or interrupted by 0 or by NRM;
RM is hydrogen, Cι-Cι_alkyl; phenyl unsubstituted or substituted by Cι-C4alkyl or by CrC4- alkoxy, or benzyl unsubstituted or substituted by Cι-C4alkyl or by CrC aIkoxy, or R14 is C2-C12alkyl interrupted one or more times by O.
L, Lt and L2 as a spacer group are, for example, a radical -Z-[(A1)a-Y]c-[(A2)b-X|d-, wherein
X, Y and Z are each independently of the others a single bond, -0-, -S-, -N(Rι6)-, -(CO)-,
-(CO)O-, -(CO)N(R16)-, -O-(CO)-, -N(R16)-(CO)- or -N(R16)-(CO)0-; t and A2 are each independently of the other C C 2alkylene, C3-Cι2cycloalkylene, pheπyl- ene, phenylene-CrC4alkylene or Cι-C4alkylene-phenylene-Cι-C4alkylene; a, b, c and d are each independently of the others a number 0 to 4; and
R16 is hydrogen, CrCι2alkyl or phenyl.
The group RG is, for example, a radical -RdC=CReRr , wherein
RGi and RG2 are each independently of the other
Figure imgf000006_0001
. and Rd, Rθ and f are each independently of the others hydrogen, Cι-C4alkyl, phenyl, (CO)0-(Cι-C4alkyl) or d-dalkylphenyl.
Cι-C24Alkyl is linear or branched and is, for example, d-do-, C Ci2-, C C8-, CrC6- or Cι-C4-alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert- butyl, pentyl, hexyl, heptyl, 2,4,4-trimethyl-pentyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and icosyl. C2-C24Alkyl interrupted one or more times by non-consecutive O, S or NRM is linear or branched, preferably linear, and is interrupted, for example, 1 -9 times, e.g. 1-7 times or once or twice by O, S or NRι4. When the radicals are interrupted by more than one 0, the O atoms are separated from one another by at least one methylene group. There are obtained, for example, structural units such as -CH2-0-CH3, -CH2CH2-0-CH2CH3, -[CH2CH2O CH3, wherein y = 1 -9, -(CH2CH20)7CH2CH3, -CH2-CH(CH3)-0-CH2-CH2CH3, -CH2-CH(CH3)-0-CH2-CH3, -CH2SCH3 or -CH2-N(CH3)2.
C2-C24Alkenyl radicals may be mono- or poly-unsaturated, and also linear or branched and are, for example, C2-C2)-, C2-C8-, C2-C6-, C4-C8-, C -C6-, Cβ-Cβ- or C2-C -alkenyl. Examples are vinyl, allyl, methallyl, 1,1-dimethylallyl, 1-butenyl, 2-butenyl, 1,3-pentadienyl, 1-hexenyl, 1- octenyl, decenyl and dodecenyl, especially allyl.
Examples of 0-, S- or N-containing 5- or 6-membered heterocyclic rings are furyl, thienyl, pyrrolyl, oxinyl, dioxinyl and pyridyl. The mentioned heterocyclic radicals can be mono- or poly-substituted, for example mono- or di-substituted, by linear or branched alkyl, e.g. methyl, ethyl, propyl, butyl, pentyl or hexyl, especially Cι-C4alkyl. Examples thereof are dimethyl- pyridyl, dimethyl pyrrolyl and methylfuryl.
Substituted phenyl is mono- to penta-substituted, e.g. mono-, di- or tri-substituted, especially mono- or di-substituted on the phenyl ring.
Halogen is fluorine, chlorine, bromine and iodine, especially chlorine and bromine, preferably chlorine.
When two of the radicals Ri, R2, R3, R4 and R5 together form C2-Ci2alkylene uninterrupted or interrupted by one or more 0, S or NR14; or when R12 and Rι3, together with the nitrogen atom to which they are bonded, form a 5- or 6-membered ring uninterrupted or interrupted by
O or by NR14, they are, for example, saturated or unsaturated rings, for example cyclopentyl, cyclohexyl, aziridinyl, pyrrolyl, pyrrolidinyl, oxazolyl, thiazolyl, pyridyl, 1,3-diazinyl, 1,2-diazinyl, piperidyl or morpholinyl.
C3-C24Cycloalkyl is linear or branched alkyl that contains at least one ring or consists solely of one ring, for example cyclopropyl, cyclopentyl, methylcyclopentyl, cyclohexyl, methyl- or dimethyl-cyclohexyl, cyclooctyl or cyclododecyl, especially cyclopentyl and cyclohexyl.
C3-C8Cycloalkyl is as defined above up to the appropriate number of carbon atoms.
Furthermore, the term cycloalkyl is to be understood as including bridged systems, such as, for exampl
Figure imgf000007_0001
C4-C2 Cycloalkyl uninterrupted or interrupted one or more times by non-consecutive O, S or NR14 is likewise, as described above, linear or branched alkyl that contains at least one ring or consists solely of one ring and is, for example, -^° , γT^ , V~N?" , ''Tpc— ,
' -Xc— etc.. C3-C24Cycloalkenyl and C5-C24cycloalkenyl correspond to the meanings given above for cycloalkyl, but the ring in question contains at least one double bond. The term also includes polyunsaturated rings and also bridged rings, e.g. cyclopropenyl, cyclopentenyl, methylcyclopentenyl, cyclohexenyl, methyl- or dimethyl-cyclohexenyl, cyclooctenyl or cyclo- dodecenyl, especially cyclopentenyl and cyclohexenyl.
C -C24Aryl alkyl is alkyl substituted by an aromatic radical. Examples are phenyl-Cι-Cι8alkyl, naphthyl-d-Cι6alkyl, anthryl-C C10alkyl, phenanthryl-d-C10alkyl, wherein the respective alkyl radical Cι-Cι8-, C1-C16-, d-Cι0- is substituted by the respective aromatic radical phenyl, naphthyl, anthryl or phenanthryl. The alkyl radicals are linear or branched and can have the meanings given above. Examples are benzyl, phenylethyl, α-methylbenzyl, phenylpentyl, phenylhexyl and α,α-dimethylbenzyl, especially benzyl, naphthylmethyl, naphthylethyl, naphthylpropyl and naphthyl-1-methylethyl, more especially naphthylmethyl. The alkyl moiety may be in either the 1- or the 2-ρosition of the naphthyl ring.
C8-C24Arylcycloalkyl is cycloalkyl substituted by an aromatic radical and is, for example, Cg-Cι6arylcycloalkyl, C9-Cι3aryIcycloalkyl, e.g. cycloalkyl bonded to one or more rings, for
example: Q , , - fTl . IX •*=! r^ etc..
The term "and/or" is intended to indicate that not only one of the defined alternatives (substituents) may be present but several different defined alternatives (substituents) may be present together, that is to say mixtures of different alternatives (substituents) may be present.
The term "at least one" is intended to define "one or more than one", e.g. one or two or three, preferably one or two.
In the description and in the patent claims, the word "containing" is to be understood as meaning that, unless expressly described to the contrary, a defined subject or a defined group of subjects is included, but without excluding any other substances not explicitly mentioned.
The expression "optionally substituted" includes both possibilities: unsubstituted and substituted.
The expression "optionally interrupted" includes both possibilities: uninterrupted and interrupted.
A is preferably . Of special interest are those compounds wherein Ri and
Figure imgf000009_0001
R2 are C C4alkyl, especially methyl, or CrC4alkoxy, especially methoxy. A is, for example, 2,4,6-trimethyl phenyl or 2,6-dimethoxyphenyl.
Preference is therefore given to compounds of formula I wherein
Figure imgf000009_0002
Ri and R2 are each independently of the other Cι-Cι2alkyl, ORn, CF3 or halogen, especially d-C alkyl, Cι-C4alkoxy, CF3 or Cl;
R3, R and R5 are each independently of the others hydrogen, Cι-C12alkyl, ORn or halogen, especially hydrogen or Cι-C alkyl.
The radical R, can be aliphatic or aromatic.
As an aliphatic radical R is preferably
Cι-Cι2alkyl unsubstituted or substituted by phenyl, CN, ORn C(0)R n, C(0)ORn or by
C(0)N(R14)2; or R is C2-Cι2alkyl interrupted one or more times by non -consecutive O and unsubstituted or substituted by phenyl, CN, ORn, C(0)Rn, C(0)ORn or by C(0)N(R14)2; or R is C2-Cι2alkenyl uninterrupted or interrupted one or more times by non -consecutive O and unsubstituted or substituted additionally by ORn, N(Rι2)(R13) or by Cι-Cι2alkyl; or R is benzyl; or R is C4-C8cycloalkyl uninterrupted or interrupted one or more times by non -consecutive
O, S or NRM and unsubstituted or substituted additionally by ORn, SRn N(Rι2)(Rι3) or by
Cι-Cι2alkyl; or R is C8-Cι2arylcycloalkyl;
R11 is hydrogen, d-d∑alkyl, C5-C6cycloalkyl, phenyl or benzyl;
R12 and R13 are each independently of the other hydrogen, Crd2alkyl, phenyl, benzyl, or
C2-Cι2alkyl interrupted one or more times by non-consecutive O atoms and unsubstituted or substituted by OH or by SH; or Rι2 and R13, together with the nitrogen atom to which they are bonded, form piperidino, morpholino or piperazino; and
R14 is hydrogen, phenyl, Cι-Ci2alkyl, or C2-Cι2alkyl interrupted one or more times by non- consecutive O atoms and unsubstituted or substituted by OH or by SH.
As an aliphatic radical, R is preferably Cι-Cι2alkyl.
As an aromatic radical, R is preferably , wherein
Figure imgf000010_0001
R6, R7, R8, Rg and R10 are each independently of the others hydrogen, Cι-Cι2alkyl, ORn, phenyl or halogen, especially Cι-C4alkyl; d-C4alkoxy, phenyl or Cl.
Preference is given to compounds of formula I wherein E is O and x is 1.
Further interesting compounds of formula I are those wherein R is phenyl, 2-methylprop-1-yl or 2,4,4-trimethyl-pent-1 -yl.
Special mention should be made of compounds of formula I wherein A is 2,6-dimethoxy- phenyl or 2,4,6-trimethylphenyl.
Special preference is given to compounds of formula I wherein L is -CH2-, -CH2CH2-0-, -0-CH2CH2-0-, -O-CH2CH2-O-CH;,-, -O-CH2- .
Interesting compounds of formula I are those wherein Rd, Rβ and Rf are each independently of the others hydrogen, phenyl, (CO)0-(C C4alkyl), for example especially (CO)OC2H5.
The following compounds of formula I are also preferred:
Figure imgf000010_0002
Figure imgf000011_0001
Preparation methods for compounds of formula I are known to the person skilled in the art and are published, for example, in GB 2 360 283 and GB 2 365 430.
The monoacylphosphine oxide (MAPO) photoinitiators of formula (I) having at least one ethylenically unsaturated C=C double bond in the molecule that are used in the process according to the invention are obtained, for example, by reaction of the corresponding metallated phosphine with a corresponding halide and subsequent oxidation: g 9 0
A— C-P- + Hal L— RG »" A— C-P-L-RG
R H2°2 R
A, R, L and RG are as defined above; Hal is a halogen atom, especially Br, 1 or Cl; M is an alkali metal, for example Li, Na, K.
The process conditions will be familiar to the person skilled to the art and can be found in the publications mentioned above.
The corresponding metallated starting materials are obtained selectively, for example, by reaction of acyl halides with dimetallated arylphosphines: o o
A— C-Hal + M-P-M "" A— C-P-M
R R
The dimetallated phosphine is obtained by reaction of the corresponding dichloride with the metal. A further possibility lies in reacting the corresponding phosphine with, for example, organolithium compounds, for example butyl lithium. The reactions are described in detail in the publications mentioned above. A further process for the preparation of MAPO of formula (I) having at least one ethylenically unsaturated C=C double bond in the molecule comprises reacting suitable phosphine intermediates in a Michaelis-Arbuzov reaction with, for example, mesitoyl chloride.
PCI2 + 2 HO-L-RG *■ lj'~l_0"L"RG A~C~Ha' — >- A-C-P-O-L-RG
R R R
A, R, L and RG are as defined above; Hal is a halogen atom, especially Br, I or Cl.
The preparation of the compounds of formulae (II), (III) and (IV) is effected analogously using the appropriate starting materials.
The invention relates likewise to compounds of formulae (F), (IP), (IIP) and (IV)
IN-Q-RG (P)
IN-Q-RG1-Q1-H (IP)
IN-Q-RG1-Q1-IN., (IIP)
IN-Q-Rd-Qi-RGϋ-Qs-IN! (IV), wherein IN and IN1 are each independently of the others a monoacylphosphine, monoacylphosphine oxide or monoacylphosphine sulfide photoinitiator group; Q, Q1 and Q2 are a single bond or a spacer group of formula — Zι-[(A1)a-Y]c-[(A2)b-X]d-, X and Y are each independently of the other a single bond, -0-, -S-, -N(Rι6)-, -(CO)-, -(CO)O-, -(CO)N(R1β)-, -O-(CO)-, -N(R1β)-(CO)- or -N(R16)-(CO)0-;
Z1 is a single bond, -S-, -(CO)-, -(CO)O-, -(CO)N(Rιβ)-, -O-(CO)-, -N(R16)-(CO)- or -N(R16)-(CO)0-;
A! and A2 are each independently of the other Cι-Cι2alkylene, C3-C12cycloalkylene, phenyl- ene, phenylene-Cι-C4alkylene or Cι-C4alkyIene-phenylene-Cι-C alkylene; a, b, c and d are each independently of the other a number 0 to 4; R16 is hydrogen, CrC1 alkyl or phenyl;
RG is a monovalent radical having at least one ethylenically unsaturated C=C bond; and RG1 and RG2 are each independently of the other a divalent radical having at least one ethylenically unsaturated C=C bond; with the proviso that compounds of formula (I) wherein the spacer group Q is methylene and at the same time RG is vinyl and compounds of formula (I) wherein the spacer group Q is a single bond and at the same time RG is allyl are excluded; and with the proviso that when Zi is a group -O(CO)-, a and c are not 0 and at the same time Aι is not a single bond.
The meanings of the definitions correspond to those indicated for formulae (I), (II), (III) and (IV); the meanings of Q are to correspond to those of L. Zi is preferably a single bond.
Also suitable in the process according to the invention are photoinitiators of the mono- and bis-acylphosphine oxide type, such as published in WO 03/068785. The invention therefore relates also to a process for the production of a strongly adherent coating on an inorganic or organic substrate, wherein a) a low-temperature plasma treatment, a corona discharge treatment or a flame treatment is carried out on the inorganic or organic substrate, b) one or more photoinitiators or mixtures of photoinitiators with monomers or/and oligomers, containing at least one ethylenically unsaturated group, or solutions, suspensions or emulsions of the afore-mentioned substances, are applied to the inorganic or organic substrate, and optionally c) using suitable methods those afore-mentioned substances are dried and/or are irradiated with electromagnetic waves, wherein there is used as photoinitiator at least one compound of formula (XX) and/or (XXI)
"2 MI H1 ϋ1'π2' R7iT c-l ~R7i (XX) R-0— C-P-Het—L— Hetj-P-C-R--' (XXI) , wherein
L-(RG3)m R- R
R70 and R7ι are each independently of the other CrCι8alkyl, C2-d8alkyl uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or by one or more substituted or unsubstituted imino groups, C2-d8alkenyl, C6-Cι2aryl, C5-d2cycloalkyl or a five- to six- membered heterocycle having oxygen, nitrogen and/or sulfur atoms, wherein the mentioned radicals may each be substituted by aryl, alkyl, aryloxy, alkyloxy, hetero atoms and/or by heterocycles;
R7ι may also be Cι-Cι8alkoxy unsubstituted or substituted by aryl, alkyl, aryloxy, alkyloxy, hetero atoms and/or by heterocycles, or R70-(C=E2)-; E2 is O, S, NR72, N-OR3 or N-NR72R73; Ei is O, S, NR72, N-OR72, N-NR72R73 or a free electron pair;
R72 is hydrogen, Cι-C4alkyl, S03H, phenyl or acetyl;
R73 is hydrogen, d-C4alkyl, C00R72, or Cθ-Cι2aryl or arylsulfonyl unsubstituted or substituted by aryl, alkyl, aryloxy, alkyloxy, hetero atoms and/or by heterocycles;
L is a spacer;
RG3 is a free-radical-polymerisable or cationically polymerisable group or a group capable of interacting with the polymer being formed; m is a natural number from 1 to 10;
R70', R7 E2' and E1' are as defined for R70> R7ι, E2 and E1 but may be different therefrom;
Heti and Het2 are each independently of the other O, S or NR 4; and
R74 are, identical or different, hydrogen or d-C4alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
Of those compounds, those shown in WO 03/068785 in Tables on pages 15 to 25 and 29 to 32, and 33 to 35, pages 42 to 67 and in the Examples and especially the compounds of Table 1, pages 81 to 83, are of special interest in the process according to the invention.
The spacer L has, for example, the meanings given above. RG3 is preferably identical to the group RG described above.
The process according to the invention is simple to carry out and allows a high throughput per unit of time, since lengthy application steps and slow crosslinking reactions are not required. The process is especially well suited to workpieces that are composed of different plastics and/or metals or types of glass and that without the pretreatment would therefore exhibit different degrees of adhesion on the different components or that in the case of a conventional primer treatment exhibit different affinities for the primer.
The photoinitiator can be applied, for example, at normal pressure - preferably after a corona treatment in a first process step, or, for example, vapour-deposited in vacuo, preferably after a plasma treatment in the first process step.
In the process according to the invention, after the photoinitiator of formula (I), (II) (III) or (IV) or the photoinitiators, or a solution or dispersion thereof in a solvent or monomer, has or have been applied to the substrate which has been plasma-, corona- or flame-pretreated and after any drying step for evaporating off any solvent used, a fixing step for the photoinitiator is carried out by exposure to UV/VIS light. In the context of the present Application, the term "drying" includes both variants, both the removal of the solvent and the fixing of the photoinitiator.
Of interest, therefore, is a process for the production of a strongly adherent coating on inorganic or organic substrates, wherein a) a low-temperature plasma treatment, a corona discharge treatment or a flame treatment is carried out on the inorganic or organic substrate, b) one or more photoinitiators of formula (I), (II), (III) and/or (IV) or mixtures of such photoinitiators with monomers or/and oligomers, containing at least one ethylenically unsaturated group, or solutions, suspensions or emulsions of the afore-mentioned substances, are applied to the inorganic or organic substrate, and c) using suitable methods those afore-mentioned substances are optionally dried and irradiated with electromagnetic waves to fix the photoinitiator.
Step c) of the above-described preferred processes is optional. For example, the drying, that is to say the removal of the solvent, is logically unecessary when no solvent has been used. The fixing of the photoinitiator in step c) of the preferred processes by irradiation with electromagnetic waves, especially UVΛ/IS radiation, is also optional. In a preferred embodiment of the process, however, the fixing of the photoinitiator by irradiation with electromagnetic waves, especially UVΛ/IS radiation, is carried out.
Suitable apparatus for drying and irradiation is described hereinbelow.
The invention relates also to a process for the production of a strongly adherent coating on an inorganic or organic substrate, wherein a) a low-temperature plasma treatment, a corona discharge treatment or a flame treatment is carried out on the inorganic or organic substrate, b) one or more photoinitiators of formula (I), (II), (III) and/or (IV) according to claim 1 or mixtures of such photoinitiators with monomers or/and oligomers, containing at least one ethylenically unsaturated group, or solutions, suspensions or emulsions of the aforementioned substances, are applied to the inorganic or organic substrate, optionally c) using suitable methods those afore-mentioned substances are dried and/or irradiated with electromagnetic waves and either d1) the substrate so precoated with photoinitiator is coated with a composition comprising at least one ethylenically unsaturated monomer or oligomer and the coating is cured by means of UVΛ/IS radiation or an electron beam; or d2) the substrate so precoated with photoinitiator is coated with a printing ink and dried; or d3) a metal, semi-metal, metal oxide or semi-metal oxide is deposited from the gaseous phase onto the substrate so precoated with photoinitiator.
Preference is given to a process for the production of a strongly adherent coating on an inorganic or organic substrate, wherein a) a low-temperature plasma treatment, a corona discharge treatment or a flame treatment is carried out on the inorganic or organic substrate, b) one or more photoinitiators or mixtures of photoinitiators with monomers or/and oligomers, containing at least one ethylenically unsaturated group, or solutions, suspensions or emulsions of the afore-mentioned substances, are applied to the inorganic or organic substrate, c) using suitable methods those afore-mentioned substances are optionally dried and irradiated with electromagnetic waves to fix the photoiniator and either d1) the substrate so precoated with photoinitiator is coated with a composition comprising at least one ethylenically unsaturated monomer or oligomer and the coating is cured by means of UVΛ/IS radiation or an electron beam? or d2) the substrate so precoated with photoinitiator is provided with a coating and dried; or d3) a metal, semi-metal, metal oxide or semi-metal oxide is deposited from the gaseous phase onto the substrate so precoated with photoinitiator.
Process step b) in each of the above-described processes is preferably carried out under normal pressure.
If, in process step b) (in each of the above-described processes), mixtures of photoinitiators with monomers or/and oligomers are used, it is preferred to use mixtures of one or more photoinitiators with monomers.
The invention relates also to a process according to either claim 1 or claim 2 wherein in addition to the compounds of formula (I), (II), (III) and/or (IV) there are used further photoinitiators (p). As further photoinitiators (p) that can be applied in addition to the compounds of formula (I), (II), (111) and/or (IV), or in addition to the compounds of formula (XX) and/or (XXI) in process step (b), there are suitable in principle any compounds and mixtures that form one or more free radicals when irradiated with electromagnetic waves. These include initiator systems consisting of a plurality of initiators and systems that function independently of one another or synergistically. In addition to coinitiators, for example amines, thiols, borates, enolates, phosphines, carboxylates and imidazoles, it is also possible to use sensitisers, for example acridines, xanthenes, thiazeπes, coumarins, thioxanthones, triazines and dyes. A description of such compounds and initiator systems can be found e.g. in Crivello J.V., Dietliker K.K., (1999): Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints, and in Bradley G. (ed.) Vol. 3: Photoinitiators for Free Radical and Cationic Polymerisation 2nd Edition, John Wiley & Son Ltd.
Such compounds and derivatives are derived, for example, from the following classes of compounds: benzoins, benzil ketals, acetophenones, hydroxyalkylphenones, aminoalkyl- phenones, acylphosphine oxides, acylphosphine sulfides, acyloxyiminoketones, alkylamino- substituted ketones, such as Michler's ketone, peroxy compounds, dinitrile compounds, halogenated acetophenones, phenylglyoxalates, dimeric phenylglyoxalates, benzophen- ones, oximes and oxime esters, thioxanthones, coumarins, ferrocenes, titanocenes, onium salts, sulfonium salts, iodonium salts, diazonium salts, borates, triazines, bisimidazoles, polysilanes and dyes. It is also possible to use combinations of the compounds from the mentioned classes of compounds with one another and combinations with corresponding coinitiator systems and/or sensitisers.
Especially interesting as additional photoinitiators (p) are compounds of formula V, VI, VII, VIII, IX, X or/and XI
- ,, (VII),
Figure imgf000018_0001
(VNI), R» (X),
Figure imgf000018_0002
O =\.R, )ζ)-'~d ∞ (χ|). wherein
R29 is hydrogen or Cι-Cι8alkoxy;
R^ is hydrogen, Cι-C18alkyl, Cι-Cι8alkoxy, -OCH2CH2-OR47, morpholino, SCH3, or a group
Figure imgf000018_0003
a, b and c are an average of 3; n is a value of from 2 to 10;
G and G4 are each independently of the other terminal groups of the polymeric unit, especially hydrogen or CH3;
R31 is hydroxy, Cι-Cι6alkoxy, morpholino, dimethylamino or -0(CH2CH20)m-C Ci6alkyl; R32 and Rss are each independently of the other hydrogen, C Cβalkyl, CrC16alkoxy or -0(CH2CH2θ)m-Cι-Cι6alkyl; or R32 and R33 are phenyl or benzyl, those radicals being unsubstituted or substituted by C Cι2alkyl; or R32 and R33, together with the carbon atom to which they are bonded, form a cyclohexyl ring; m is a number from 1 to 20; but R31, R32 and RM are not all simultaneously C C18alkoxy or -0(CH2CH20)m-CrC16alkyl; Ri is hydrogen, — C-C=CH2 or — C-C=CH2
RM, 36, R37 and R38 are each independently of the others hydrogen or methyl; RK and R3!3 are hydrogen, methyl or phenylthio, wherein the phenyl ring of the phenylthio radical is unsubstituted or substituted in the 4-, 2-, 2,4- or 2,4,6-position(s) by C C4alkyl; R40 and R41 are each independently of the other CrC20alkyl, cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenylyl, those radicals being unsubstituted or substituted by halogen, C Cι2alkyl, d-C12alkoxy, C Cι2alkylthio or by NR52R53. or R40 and R41 are a S- or N- containing 5- or 6-membered heterocyclic ring or -(CO)R42;
R42 is cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenylyl, those radicals being unsubstituted or substituted by halogen, d-dalkyl or/and by Crdalkoxy, or R 2 is a S- or N- containing 5- or 6-membered heterocyclic ring;
R43 and R4 are each independently of the other cyclopentadieπyl unsubstituted or mono-, di- or tri-substituted by Cι-Cι8alkyl, d-Cι8alkoxy, cyclopentyl, cyclohexyl or by halogen; R45 and R46 are each independently of the other phenyl which is substituted by fluorine atoms or CF3 in at least one of the two positions ortho to the titanium-carbon bond and may contain, as further substituents at the aromatic ring, polyoxaalkyl or pyrrolinyl unsubstituted or substituted by one or two Cι-Ci2alkyl, di(Cι-Ci2alkyl)aminomethyl, morpholinomethyl, C2-C4alkenyl, methoxy methyl, ethoxymethyl, trimethylsilyl, formyl, methoxy or phenyl substituents,
Figure imgf000019_0001
R48, 49 and R50 are each independently of the others hydrogen, halogen, C2-Ci2alkenyl, d-Cι2alkoxy, C2-C12alkoxy interrupted by from one to four O atoms, cyclohexyloxy, cyclopentyloxy, phenoxy, benzyloxy, or phenyl or biphenylyl each unsubstituted or substituted by d-dalkoxy, halogen, phenylthio or by -dalkylthio, wherein R48 and R5o are not both simultaneously hydrogen and in the radical
at least one radical R48 or R50 is Cι-Cι2alkoxy, C2-Cι2alkoxy interrupted by
Figure imgf000020_0001
from one to four O atoms, cyclohexyloxy, cyclopentyloxy, phenoxy or benzyloxy;
G5 is O, S or NR5ι; and
Rs-\ is C C8alkyl, phenyl or cyclohexyl;
R52 and Rs3 are each independently of the other hydrogen; Ci-Caalkyl uninterrupted or interrupted by O atoms and unsubstituted or substituted by OH or by SH; or R52 and R53 are
C2-Cι2alkenyl, cyclopentyl, cyclohexyl, benzyl, phenyl;
RM is hydrogen,
Figure imgf000020_0002
or a group ;
Figure imgf000020_0003
R55, δs, R571 R58 and R59 are each independently of the others hydrogen; Ci-Caalkyl which is unsubstituted or substituted by OH, d-C4alkoxy, phenyl, naphthyl, halogen or by CN and may be interrupted by one or more O atoms; or R55, Rx, R5 , Rsβ and Rsg are d-dalkoxy, d-dalkylthio or NR52R53;
Y! is a divalent aliphatic or aromatic radical, especially Cι-d2alkylene; x is 0 or 1 ;
R∞ is phenyl, naphthyl, or, when x is 0, 9H-carbazol-3-yl, or (9-oxo-9H-thioxantheπ-2-yl)-, all those radicals being unsubstituted or substituted by one or more SRe3, ORw, NR52R53, halogen, Ci-Caalkyl, phenyl, benzyl, -(CO)-CrC4alkyl, -(CO)-phenyl or -(CO)-phenylene- Cι-C4alkyl substituents; ei is C4-C9cycloalkanoyl; d-C^alkanoyl unsubstituted or substituted by one or more halogen, phenyl or CN substituents; or R6ι is C4-Cβalkenoyl, with the proviso that the double bond is not conjugated with the carbonyl group; or R6ι is benzoyl unsubstituted or substituted by one or more d-C6alkyl, halogen, CN, OR64, SRe3 or NR52R53 substituents; or R6ι is C2-C8alkoxycarbonyl, benzyloxycarbonyl; or phenoxycarbonyl unsubstituted or substituted by one or more CrC6alkyl or halogen substituents;
R82 is hydrogen, phenyl or benzoyl, the radicals phenyl and benzoyl being unsubstituted or substituted by Cι-C6alkyl, phenyl, halogen, OR64, SR^ or by NR52RS3; or R62 is Ci-Caalkyl or C2-Cι2alkoxycarbonyl, the radicals d-C2oalkyl and C2-Ci2alkoxycarbonyl being unsubstituted or substituted by OH and uninterrupted or interrupted by one or more O atoms; or R6 is
C2-C20alkanoyl, benzyl, benzyl-(CO)-, CrC6alkyl-S02- or phenyI-S02-;
Rra and R6 are each independently of the other hydrogen or CrCι2alkyl unsubstituted or substituted by OH, SH, CN, phenyl, (CO)0-Cι-C4alkyl, 0(CO)-Cι-C4aIkyl, COOH, O(CO)- phenyl, and such unsubstituted or substituted Cι-C12alkyl may be interrupted by one or more O atoms; or Rrø and R64 are cyclohexyl, or phenyl unsubstituted or substituted by
Ci-Caalkyl, d-Cι2alkoxy or by halogen, or phenyl-C C3alkyl;
RK. Rββ and R67 are each independently of the others hydrogen, CrC4alkyl, d-C4haloalkyl,
CrC4alkoxy, chlorine or N(Cι-C4alkyl)2;
Res is hydrogen, Cι-C4alkyl, d-C haloalkyl, phenyl, N(d-C4alkyl)2, COOCH3,
Figure imgf000021_0001
o u or - -0O--CC--cC --0O--((CCHH22))44-- --0O--CC--CC--0O ^^ c ^^ ; or RB8 and R67 together are -S-. H, i- Jπ H, xxo
C C2oAlkyl has the meanings given above up to the appropriate number of carbon atoms. Cι-Cι8Alkoxy is, for example, branched or unbranched alkoxy, e.g. methoxy, ethoxy, n- propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2,4,4-trimethyl-pent-1-yloxy, 2-ethyl hexyloxy, nonyloxy, decyloxy, dodecyloxy or octadecyloxy. C Cι6-, Cι-C12- and Cι-C4-alkoxy have the meanings given above up to the respective number of carbon atoms.
Cι-Cι Alkylthio is linear or branched and is, for example, Cι-C8-, Cι-C6- or Cι-C4-a]kylthio, for example methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec- butylthio or tert-butylthio, preferably methylthio.
Substituted phenyl is, for example, mono- to penta-substituted, for example mono-, di- or tri- substituted, on the phenyl ring.
When R40, R41 and R42 are a S- or N-containing 5- or 6-membered heterocyclic ring, they are, for example, thienyl, pyrrolyl or pyridyl.
C2-Ci2Alkenyl is linear or branched, can be mono- or poly-unsaturated and is, for example, allyl, methallyl, 1,1-dimethylallyl, 1-butenyl, 2-butenyl, 1,3-pentadienyl, 1-hexenyl or 1-octenyl, especially allyl. C2-C4Alkenyl is, for example, allyl, methallyl, 1-butenyl or 2-butenyl. Halogen is fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine. The term polyoxaalkyl includes C2-C2oalkyl interrupted by from 1 to 9 O atoms and denotes, for example, structural units such as CH3-0-CH2-, CH3CH2-0-CH2CH2-, CH30[CH2CH20]2-, wherein z = 1-9, -(CH2CH20)7CH2CH3, -CH2-CH(CH3)-0-CH2-CH2CH3.
A divalent aliphatic or aromatic radical Yi is, for example, Ci-dsalkylene, linear or branched, uninterrupted or interrupted by one or more O atoms and unsubstituted or substituted by OH; or cycloalkylene, e.g. cyclohexylene, the term cycloalkylene also including radicals such as, for example, -CH2-cyclohexylene-CH2-. A corresponding aromatic radical is, for example, phenylene, naphthylene, biphenylene, all unsubstituted or substituted, and all optionally additionally substituted at the bonds by alkylene in a manner analogous to that described for cycloalkylene.
Rβo as substituted 9H-carbazol-3-yl is preferably substituted by C Cι2alkyl, and -(CO)- phenyl or -(CO)-phenylene-Cι-C4alkyl, substitution being possible at one of the aromatic rings and at the N atom. R6o is in this case especially a radical of formula
COOσO"
A preferred compound of formula X wherein R6o is substituted 9H-carbazol-3-yl is
Figure imgf000022_0001
When Raβ and R67 together are -S-, the following structure wherein Re
Figure imgf000022_0002
and RRB are as defined is obtained.
In the compounds of formulae V; VI; VII; VIII; IX, X and XI, preferably
R30 is hydrogen, -OCH2CH2-OR47, morpholino, SCH3, a group H2C=C— or a group
R3ι is hydroxy, Ci-Ciealkoxy, morpholino or dimethylamino;
R32 and R∞ are each independently of the other Ci-dalkyl, phenyl, benzyl or Cι-Cιθalkoxy, or R32 and R∞, together with the carbon atom to which they are bonded, form a cyclohexyl ring; o R,7 is hydrogen or — c-c-=cHa ;
RM, RM and R36 and R3 , R38 and R39 are hydrogen or d-dalkyl;
R40 is Ci-Caalkyl, unsubstituted phenyl, or phenyl substituted by Ci-Caalkyl or/and by
Cι-Cι2alkoxy;
R« is (CO)R 2; and
R 2 is phenyl substituted by Cι-C4alkyl or/and by C -C4alkoxy;
R55, R56, R57, RSB and R59 are hydrogen;
R54 is the group
Figure imgf000023_0001
Y1 is -CH2CH2-0-CH2CH2-: x is 1;
RBO is phenyl substituted by SR63 or f |'
R6ι is benzoyl; si is hexyl; and Rra is phenyl.
Preferred compounds of formulae V, VI, VII, VIII, IX, X and XI are α-hydroxycyclohexyl- phenyl-ketone or 2-hydroxy-2-methyl-1-phenyl-propanone, (4-methylthiobenzoyl)-1-methyI- 1-morpholino-ethane, (4-morpholino-benzoyl)-1-benzyl-1-dimethylamino-propane, (4-morph- olino-benzoyl)-1-(4-methylbenzyl)-1-dimethylamino-propane, (3,4-dimethoxy-benzoyl)-1- benzyl-1-dimethylamino-propane, beπzil dimethyl ketal, (2,4,6-trimethylbenzoyl)-dipheπyl- phosphine oxide, bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethyl-pent-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenyl-phosphine oxide or bis(2,4,6-trimethylbenzoyl)-(2,4- dipentyloxyphenyl)phosphiπe oxide, 5,5'-oxodi(ethyleneoxydicarboπylphenyl) and dicyclo- pentadienyl-bis(2,6-difluoro-3-pyrrolo)titanium, and also benzophenone, 4-phenylbenzo- phenone, 3-methyl-4'-phenylbenzophenone, 4-methoxybenzophenone, 4,4'-dimethoxy- benzophenone, 4,4'-dimethylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dimethyl- aminobenzophenone, 4,4'-diethylaminobenzophenone, 4-methylbenzophenone, 2,4,6- trimethylbenzophenone, 2,4,6-trimethyl-4'-phenylbenzophenone, 4-(4-methylthiophenyl)- benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, methyl 2-benzoylbenzoate, 4-(2- hydroxyethylthio)-benzophenone, 4-(4-tolylthio)benzophenone, 4-benzoyl-N,N,N-trimethyl- benzenemethanaminium chloride, • 2-hydroxy-3-(4-benzoylphenoxy)-N,N,N-trimethyl-1- propanaminium chloride monohydrate, 4-(13-acryloyl-1 ,4,7, 10,13-pentaoxatridecyl)-benzo- phenone, 4-benzoyI-N,N-dimethyl-N-[2-(1-oxo-2-propenyl)oxy]ethyl-benzenemethan- aminiu chloride; 2,2-dichloro-1-(4-phenoxyphenyl)-ethanone, 4,4'-bis(chloromethyI)- benzophenone, 4-methylbenzophenone, 2-methyIbenzophenone, 3-methylbenzophenone, 4-chlorobenzophenone,
0.cΛ0.c_? r 0_(oH2) ι 0_§_c_00-c )
■ wherein g, h and i are an average of 3
Figure imgf000024_0001
(SiMFPI2); and also 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanth- oπe, 3-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone.
Preference is given to compounds as additional photoinitiators (p) wherein in formula V R32 and R33 are each independently of the other Cι-C6alkyl or, together with the carbon atom to which they are bonded, form a cyclohexyl ring and R31 is hydroxy.
When mixtures of compounds of formula I, II, III and/or IV with compounds of formula V, VI, VII, VIII, IX, X and/or XI are used, the proportion of compounds of formula I, II, III and/or IV in admixture with compounds of formula V, VI, VII, VIII, IX, X and/or XI is from 5 to 99 %, e.g. 20-80 %, preferably 25 to 75 %. Preferred are mixtures comprising compounds of formula 1 and compounds of formula VII wherein
Rω is phenyl unsubstituted or substituted by from one to three Cι-Cι2alkyl or/and
Cι-Cι2alkoxy substituents, or d-C12alkyl;
Rn Is the group (CO)R 2 or phenyl; and
R42 is phenyl substituted by from one to three Cι-C4alkyl or Ci-dalkoxy substituents.
The preparation of the compounds of formulae V, VI, VII, VIII, IX, X and XI is generally known to the person skilled in the art and some of the compounds are commercially available. The preparation of oligomeric compounds of formula V is described, for example, in EP 161 463. A description of the preparation of compounds of formula VI can be found, for example, in EP 209831. The preparation of compounds of formula VII is disclosed, for example, in EP 7508, EP 184 095 and GB 2 259 704. The preparation of compounds of formula VIII is described, for example, in EP 318 894, EP 318 893 and EP 565488. Compounds of formula IX are known from US 6 048 660 and compounds of formula X are known from GB 2 339 571 or WO 02/100903. Compounds of formula XI can be obtained, for example, analogously to the methods described for the compounds according to the invention. Some compounds of formula XI are also commercially obtainable.
Possible ways of obtaining plasmas under vacuum conditions have been described frequently in the literature. The electrical energy can be coupled in by inductive or capacitive means. It may be direct current or alternating current; the frequency of the alternating current may range from a few kHz up into the MHz range. A power supply in the microwave range (GHz) is also possible.
The principles of plasma production and maintenance are described, for example, in the review articles by A. T. Bell and H. Suhr mentioned above.
As primary plasma gases it is possible to use, for example, He, argon, xenon, N2, 02, H2, steam or air, and also mixtures of those compounds.
The process according to the invention is not sensitive per se in respect of the coupling-in of the electrical energy. The process can be carried out batchwise, for example in a rotating drum, or continuously in the case of films, fibres or woven fabrics. Such methods are known and are described in the prior art.
The process can also be carried out under corona discharge conditions. Corona discharges are produced under normal pressure conditions, the ionised gas most frequently used being air. In principle, however, other gases and mixtures are also possible, as described, for example, in COATING Vol. 2001, No. 12, 426, (2001). The advantage of air as ionisation gas in corona discharges is that the operation can be carried out in an apparatus open to the outside and, for example, a film can be drawn through continuously between the discharge electrodes. Such process arrangements are known and are described, for example, in J. Adhesion Sci. Technol. Vol 7, No. 10, 1105, (1993). Three-dimensional workpieces can be treated with a free plasma jet, the contours being followed with the assistance of robots.
In the process according to the invention in process step a), the treatment with a corona discharge is preferred.
The flame treatment of substrates is known to the person skilled in the art. Corresponding industrial apparatus, for example for the flame treatment of films, is commercially available. In such a treatment, a film is conveyed on a cooled cylindrical roller past the flame- treatment apparatus, which consists of a chain of burners arranged in parallel, usually along the entire length of the cylindrical roller. Details can be found in the brochures of the manufacturers of flame-treatment apparatus (e.g. esse Cl, flame treaters, Italy). The parameters to be chosen are governed by the particular substrate to be treated. For example, the flame temperatures, the flame intensity, the dwell times, the distance between substrate and burner, the nature of the combustion gas, air pressure, humidity, are matched to the substrate in question. As flame gases it is possible to use, for example, methane, propane, butane or a mixture of 70 % butane and 30 % propane.
The inorganic or organic substrate to be treated can be in any solid form. The substrate is preferably in the form of a woven fabric, a fibre, a film or a three-dimensional workpiece. The substrate may be, for example, a thermoplastic, elastomeric, inherently crosslinked or crosslinked polymer, a metal oxide, a ceramic material, glass, metal, leather or textile. The pretreatment of the substrate in the form of plasma-, corona- or flame-treatment can be carried out, for example, immediately after the extrusion of a fibre or film, and also directly after film-drawing.
The inorganic or organic substrate is preferably a thermoplastic, elastomeric, inherently crosslinked or crosslinked polymer, a metal oxide, a ceramic material, a glass or a metal, especially a thermoplastic, elastomeric, inherently crosslinked or crosslinked polymer.
Examples of thermoplastic, elastomeric, inherently crosslinked or crosslinked polymers are listed below.
1. Polymers of mono- and di-olefins, for example polypropylene, polyisobutylene, poly- butene-1 , poly-4-methylpentene-1 , polyisoprene or polybutadiene and also polymerisation products of cyclo-olefins, for example of cyclopentene or norbornene; and also polyethylene (which may optionally be crosslinked), for example high density polyethylene (HDPE), high density polyethylene of high molecular weight (HDPE-HMW), high density polyethylene of ultra-high molecular weight (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), and linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
Polyolefins, that is to say polymers of mono-olefins, as mentioned by way of example in the preceding paragraph, especially polyethylene and polypropylene, can be prepared by various processes, especially by the following methods: a) by free-radical polymerisation (usually at high pressure and high temperature); b) by means of a catalyst, the catalyst usually containing one or more metals of group IVb, Vb, Vlb or VIII. Those metals generally have one or more ligands, such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls, which may be either π- or σ-coordinated. Such metal complexes may be free or fixed to carriers, for example to activated magnesium chloride, titanium(lll) chloride, aluminium oxide or silicon oxide. Such catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be active as such in the polymerisation or further activators may be used, for example metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyl oxanes, the metals being elements of group(s) la, Ha and/or Ilia. The activators may have been modified, for example, with further ester, ether, amine or silyl ether groups. Such catalyst systems are usually referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or Single Site Catalysts (SSC)
2 Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE)
3 Copolymers of mono- and di-olefins with one another or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/butene-1 copolymers, propylene/isobutylene copolymers, ethylene/butene-1 copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/- alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and copolymers thereof with carbon monoxide, or ethylene/acrylic acid copolymers and salts thereof (lonomers), and also terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidenenorbornene, and also mixtures of such copolymers with one another or with polymers mentioned under 1), for example polypropylene-ethylene/propylene copolymers, LDPE-ethylene/vinyl acetate copolymers, LDPE-ethylene/acrylic acid copolymers, LLDPE-ethylene/vinyl acetate copolymers, LLDPE- ethylene/acrylic acid copolymers and alternately or randomly structured polyalkylene-carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides
4 Hydrocarbon resins (for example Cs-C9) including hydrogenated modifications thereof (for example tackifier resins) and mixtures of polyalkylenes and starch
5 Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene)
6 Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitπle, styrene/alkyl methacrylate, styrene/buta- diene/alkyl acrylate and methacrylate, styrene/maleic anhydride, styrene/acrylonitπle/methyl acrylate, high-impact-strength mixtures consisting of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer, and also block copolymers of styrene, for example styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene-butylene/styrene or styrene/ethylene-propylene/- styrene
7 Graft copolymers of styrene or α-methylstyrene, for example styrene on polybuta- diene, styrene on polybutadiene/styrene or polybutadiene/acrylonitπle copolymers, styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleic acid imide on polybutadiene; styrene and maleic acid imide on polybutadiene, styrene and alkyl acrylates or alkyl methacrylates on polybutadiene, styrene and acrylonitrile on ethylene/propylene/diene terpolymers, styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, and mixtures thereof with the copolymers mentioned under 6), such as those known, for example, as so-called ABS, MBS, ASA or AES polymers.
8. Halogen-containing polymers, for example polychloroprene, chlorinated rubber, chlorinated and brominated copolymer of isobutylene/isoprene (halobutyl rubber), chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and co-polymers, especially polymers of halogen- containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; and copolymers thereof, such as vinyl chloride/- vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate.
9. Polymers derived from α,β-unsaturated acids and derivatives thereof, such as poly- acrylates and polymethacrylates, or polymethyl methacrylates, polyacrylamides and poly- acrylonitriles impact-resistant-modified with butyl acrylate.
10. Copolymers of the monomers mentioned under 9) with one another or with other unsaturated monomers, for example acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate copolymers, acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
11. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate or maleate, poly- vinylbutyral, polyallyl phthalate, polyallylmelamine; and the co polymers thereof with olefins mentioned in Point 1.
12. Homo- and co-polymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
13. Polyacetals, such as polyoxymethylene, and also those polyoxymethylenes which contain comonomers, for example ethylene oxide; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
14. Polyphenylene oxides and sulfides and mixtures thereof with styrene polymers or polyamides. 15. Polyurethanes derived from polyethers, polyesters and polybutadienes having terminal hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates on the other hand, and their initial products.
16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides derived from m-xylene, diamine and adipic acid; polyamides prepared from hexa- methylenediamine and iso- and/or tere-phthalic acid and optionally an elastomer as modifier, for example poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m- phenylene isophthalamide. Block copolymers of the above-mentioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, for example with polyethylene glycol, polypropylene glycol or polytetramethylene glycol. Also polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing ("RIM polyamide systems").
17. Polyureas, polyimides, polyamide imides, polyether imides, polyester imides, poly- hydantoins and polybenzimidazoles.
18. Polyesters derived from dicarboxylic acids and dialcohols and/or from hydroxy- carboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene' terephthalate, poly-1 ,4-dimethylolcyclohexane terephthalate, polyhydroxy- benzoates, and also block polyether esters derived from polyethers with hydroxyl terminal groups; and also polyesters modified with polycarbonates or MBS.
19. Polycarbonates and polyester carbonates.
20. Polysulfones, polyether sulfones and polyether ketones.
21. Crosslinked polymers derived from aldehydes on the one hand and phenols, urea or melamine on the other hand, such as phenol-formaldehyde, urea-formaldehyde and mela- mine-formaldehyde resins.
22. Drying and non-drying alkyd resins.
23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols, and also vinyl compounds as crosslinking agents, and also the halogen-containing, difficultly combustible modifications thereof.
24. Crosslinkable acrylic resins derived from substituted acrylic esters, e.g. from epoxy acrylates, urethane acrylates or polyester acrylates. 25. Alkyd resins, polyester resins and acrylate resins that are crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.
26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of bisphenol A diglycidyl ethers, bisphenol F diglycidyl ethers, that are crosslinked using customary hardeners, e.g. anhydrides or amines with or without accelerators.
27. Natural polymers, such as cellulose, natural rubber, gelatin, or polymer- homologously chemically modified derivatives thereof, such as cellulose acetates, propionates and butyrates, and the cellulose ethers, such as methyl cellulose; and also colophonium resins and derivatives.
28. Mixtures (polyblends) of the afore-mentioned polymers, for example PP/EPDM, poly- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA PPO, PBT/PC/ABS or PBT/PET/PC.
The substrate can be, for example, a substrate as used in the field of commercial printing, for sheet-fed intaglio printing, sheetfed gravure printing, sheetfed offset printing or endless printing, posters, calendars, forms, labels, packaging films, tapes, credit cards, furniture profiles efc..
The substrate is not confined to use in the non-nutrition sector. The substrate may also be, for example, a material for use in the field of nutrition, e.g. as packaging for foodstuffs, cosmetics, medicaments, efc..
Where substrates have been pretreated according to processes of the invention it is also possible, for example, for substrates that usually have poor compatibility with one another to be adhesively bonded to one another or laminated.
Within the context of the present invention, paper should also be understood as being an inherently crosslinked polymer, especially in the form of card(board), which can additionally be coated with e.g. Teflon®. Such substrates are, for example, commercially available. The thermoplastic, crosslinked or inherently crosslinked plastics is preferably a polyolefin, polyamide, polyacrylate, polycarbonate, polystyrene or an acrylic/melamine, alkyd or poly- urethane coating.
Polycarbonate, polyethylene and polypropylene are especially preferred.
The plastics may be, for example, in the form of films, injection-moulded articles, extruded workpieces, fibres, felts or woven fabrics.
As inorganic substrates there come into consideration especially glass, ceramic materials, metal oxides and metals. They may be silicates and semi-metal or metal oxide glasses which are preferably in the form of layers or in the form of powders preferably having average particle diameters of from 10 nm to 2000 μm. The particles may be dense or porous. Examples of oxides and silicates are Si02, Ti02, Zr02, MgO, NiO, W03, Al 03, La203, silica gels, clays and zeolites. Preferred inorganic substrates, in addition to metals, are silica gels, aluminium oxide, titanium oxide and glass and mixtures thereof.
As metal substrates there come into consideration especially Fe, Al, Ti, Ni, Mo, Cr and steel alloys.
After the application of the photoinitiator in process step b), the workpiece can be stored or immediately processed further, there being applied by means of known technology either (preferred) a radiation-curable coating containing ethylenically unsaturated bonds, or a coating that dries/cures in some other way, e.g. a printing ink. This can be effected by means of pouring, immersion, spraying, coating, knife application, roller application or spin- coating.
The unsaturated compounds of the radiation-curable composition in process step d1) may contain one or more ethylenically unsaturated double bonds. They may be lower molecular weight (monomeric) or higher molecular weight (oligomeric). Examples of monomers having a double bond are alkyl and hydroxyalkyl acrylates and methacrylates, e.g. methyl, ethyl, butyl, 2-ethylhexyl and 2-hydroxyethyl acrylate, isobornyl acrylate and methyl and ethyl methacrylate. Also of interest are silicone acrylates. Further examples are acrylo nitrile, acrylamide, methacrylamide, N-substituted (meth)acrylamides, vinyl esters, such as vinyl acetate, vinyl ethers, such as isobutyl vinyl ether, styrene, alkyl- and halo-styrenes, N- vinylpyrrolidone, vinyl chloride and vinylidene chloride.
Examples of monomers having more than one double bond are ethylene glycol diacrylate, 1 ,6-hexanediol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, hexamethylene glycol diacrylate and bisphenol A diacrylate, 4,4'-bis(2-acryloyloxyethoxy)diphenylpropane, trimethylol- propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, vinyl acrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, tris(hydroxyethyl) isocyanurate triacrylate (Sartomer 368; from Cray Valley) and tris(2- acryloylethyl) isocyanurate.
It is also possible in radiation-curable systems to use acrylic esters of alkoxylated polyols, for example glycerol ethoxylate triacrylate, glycerol propoxylate triacrylate, tri methylol- propaneethoxylate triacrylate, trimethylolpropanepropoxylate triacrylate, pentaerythritol ethoxylate tetraacrylate, pentaerythritol propoxylate triacrylate, pentaerythritol propoxylate tetraacrylate, neopentyl glycol ethoxylate diacrylate or neopentyl glycol propoxylate diacrylate. The degree of alkoxylation of the polyols used may vary.
Examples of higher molecular weight (oligomeric) polyunsaturated compounds are acrylated epoxy resins, acrylated or vinyl-ether- or epoxy-group-containing polyesters, polyurethanes and polyethers. Further examples of unsaturated oligomers are unsaturated polyester resins, which are usually produced from maleic acid, phthalic acid and one or more diols and have molecular weights of about from 500 to 3000. In addition it is also possible to use vinyl ether monomers and oligomers, and also maleate-terminated oligomers having polyester, polyurethane, polyether, polyvinyl ether and epoxide main chains. In particular, combinations of vinyl-ether-group-carrying oligomers and polymers, as described in WO 90/01512, are very suitable, but copolymers of monomers functionalised with maleic acid and vinyl ether also come into consideration. Such unsaturated oligomers can also be termed prepolymers.
Especially suitable are, for example, esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides, and polymers having ethylenically unsaturated groups in the chain or in side groups, e.g. unsaturated polyesters, polyamides and polyurethanes and copoly- mers thereof, alkyd resins, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers having (meth)acrylic groups in side chains, and also mixtures of one or more such polymers.
Examples of unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid and unsaturated fatty acids such as linolenic acid or oleic acid. Acrylic and methacrylic acid are preferred.
Suitable polyols are aromatic and especially aliphatic and cycloaliphatic polyols. Examples of aromatic polyols are hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-di(4-hydroxyphenyl)pro- pane, and novolaks and resols. Examples of polyepoxides are those based on the said polyols, especially the aromatic polyols and epichlorohydrin. Also suitable as polyols are polymers and copolymers that contain hydroxyl groups in the polymer chain or in side groups, e.g. polyvinyl alcohol and copolymers thereof or polymethacrylic acid hydroxyalkyl esters or copolymers thereof. Further suitable polyols are oligoesters having hydroxyl terminal groups.
Examples of aliphatic and cycloaliphatic polyols include alkylenediols having preferably from 2 to 12 carbon atoms, such as ethylene glycol, 1 ,2- or 1 ,3-propanediol, 1,2-, 1,3- or 1 ,4- butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycols having molecular weights of preferably from 200 to 1500, 1 ,3- cyclopentanediol, 1 ,2-, 1,3- or 1 ,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol, tris(β-hydroxyethyl)amine, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol.
The polyols may have been partially or fully esterified by one or by different unsaturated carboxylic acid(s), it being possible for the free hydroxyl groups in partial esters to have been modified, for example etherified, or esterified by other carboxylic acids.
Examples of esters are: trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacryl- ate, 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, dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate, tripentaerythritol octamethacrylate, pentaerythritol diitaconate, dipentaerythritol trisitaconate, dipentaerythritol pentaitaconate, dipentaerythritol hexaitaconate, ethylene glycol diacrylate, 1 ,3-butanediol diacrylate, 1 ,3-butanediol dimethacrylate, 1 ,4-butanediol diitaconate, sorbitol triacrylate, sorbitol tetraacrylate, pentaerythritol-modified triacrylate, sorbitol tetramethacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, oligoester acrylates and methacrylates, glycerol di- and tri-acrylate, 1 ,4-cyclohexane diacrylate, bisacrylates and bismethacrylates of polyethylene glycol having a molecular weight of from 200 to 1500, and mixtures thereof. Also suitable as a component are the amides of identical or different unsaturated carboxylic acids and aromatic, cycloaliphatic and aliphatic polyamines having preferably from 2 to 6, especially from 2 to 4, amino groups. Examples of such polyamines are ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-, 1,3- or 1 ,4-butylenediamine, 1,5-pentylenediamiπe, 1,6- hexylenediamine, octylenediamine, dodecylenediamine, 1,4-diamino-cyclohexane, isophor- onediamine, phenylenediamine, bisphenylenediamine, di-β-aminoethyl ether, diethylenetri- amine, triethylenetetramine and di(β-aminoethoxy)- and di(β-aminopropoxy)-ethane. Further suitable polyamines are polymers and copolymers which may have additional amino groups in the side chain and oligoamides having amino terminal groups. Examples of such unsaturated amides are: methylene bisacrylamide, 1,6-hexamethylene bisacrylamide, diethylenetriamine trismethacrylamide, bis(methacrylamidopropoxy)ethane, β-methacryl- amidoethyl methacrylate and N-[(β-hydroxyethoxy)ethyl]-acrylamide.
Suitable unsaturated polyesters and polyamides are derived, for example, from maleic acid and diols or diamines. The maleic acid may have been partially replaced by other dicarboxylic acids. They may be used together with ethylenically unsaturated comonomers, e.g. styrene. The polyesters and polyamides may also be derived from dicarboxylic acids and ethylenically unsaturated diols or diamines, especially from those having longer chains of e.g. from 6 to 20 carbon atoms. Examples of polyurethanes are those composed of saturated diisocyanates and unsaturated diols or unsaturated diisocyanates and saturated diols.
Polybutadiene and polyisoprene and copolymers thereof are known. Suitable comonomers include, for example, olefins, such as ethylene, propene, butene, hexene, (meth)acrylates, acrylonitrile, styrene and vinyl chloride. Polymers having (meth)acrylate groups in the side chain are likewise known. Examples are reaction products of novolak-based epoxy resins with (meth)acrylic acid; homo- or co-polymers of vinyl alcohol or hydroxyalkyl derivatives thereof that have been esterified with (meth)acrylic acid; and homo- and co-polymers of (meth)acrylates that have been esterified with hydroxyalkyl (meth)acrylates. Also suitable are acrylates that have been modified by the reaction with primary or secondary amines, as described e.g. in US 3844 916, in EP 280 222, in US 5482 649 or in US 5 734 002. Such amine-modified acrylates are also termed aminoacrylates. Amino- acrylates are obtainable e.g. under the name RTMEBECRYL 80, RTMEBECRYL 81, RTMEBECRYL 83, RTMEBECRYL 7100 from UCB Chemicals, under the name R™Laromer PO 83F, RTMLaromer PO 84F, R™Laromer PO 94F from BASF, under the name RTMPHOTOMER 4775 F, T PHOTOMER 4967 F from Cognis or under the name RTMCN501, R™CN503, RTMCN550 from Cray Valley.
In the context of the present Application the term (meth)acrylate includes both the acrylate and the methacrylate.
An acrylate or methacrylate compound is especially used as the mono- or poly-ethylenically unsaturated compound.
Very special preference is given to polyunsaturated acrylate compounds, such as have already been mentioned above.
Special preference is given to a process wherein at least one of the ethylenically unsaturated monomers or oligomers of the radiation-curable composition is a mono-, di-, tri- or tetra-functional acrylate or methacrylate.
The composition in step d1), in addition to comprising at least one ethylenically unsaturated monomer or oligomer, preferably comprises at least one further photoinitiator or coinitiator for the curing with UVΛ/IS radiation.
The invention therefore relates also to a process wherein in process step d1) a photo- polymerisable composition, comprising at least one ethylenically unsaturated monomer or/and oligomer and at least one photoinitiator and/or coinitiator, is applied to the pretreated substrate and cured by means of UVΛ/IS radiation.
In the context of the present invention, UVΛ/IS radiation is to be understood as being electromagnetic radiation in a wavelength range from 150 nm to 700 nm. Preference is given to the range from 250 nm to 500 nm. Suitable lamps are known to the person skilled in the art and are commercially available.
The photosensitivity of the compositions according to process step d1) usually extends from approximately 150 nm to approximately 600 nm (UV field). A large number of the most varied kinds of light source may be used. Both point sources and planiform radiators (lamp arrays) are suitable. Examples are: carbon arc lamps, xenon arc lamps, medium-pressure, super-high-pressure, high-pressure and low-pressure mercury radiators doped, where appropriate, with metal halides (metal halide lamps), microwave-excited metal vapour lamps, excimer lamps, superactinic fluorescent tubes, fluorescent lamps, argon incandescent lamps, flash lamps, photographic floodlight lamps, light-emitting diodes (LED), electron beams and X-rays. The distance between the lamp and the substrate to be irradiated may vary according to the intended use and the type and strength of the lamp and may be, for example, from 2 cm to 150 cm. Also suitable are laser light sources, for example excimer lasers, such as Krypton-F lasers for irradiation at 248 nm. Lasers in the visible range may also be used. This method may be used to produce printed circuits in the electronics industry, lithographic offset printing plates or relief printing plates and also photographic image-recording materials.
The above description of suitable radiation sources relates both to irradiation step c) (fixing of the photoinitiator) in the process according to the invention and the procedure of process step d1) (curing of the photocurable composition).
The curing of the composition applied in process step d1) or d2) may, in addition, likewise be carried out with daylight or with light sources equivalent to daylight.
Advantageously the dose of radiation used in process step c) is e.g. from 1 to 1000 mJ/cm2, such as 1-800 mJ/cm2, or, for example, 1-500 mJ/cm2, e.g. from 5 to 300 mJ/cm2, preferably from 10 to 200 mJ/cm2.
As photoinitiator in the radiation-curable compositions according to process step d1) it is possible to use compounds of formula I, II, III or IV or any initiators and initiator systems known from the prior art.
In those compositions preference is given to the use of photoinitiators without unsaturated groups. Typical examples are mentioned below, which can be used either singly or in admixture with one another. For example, benzophenones, benzophenone derivatives, acetophenone, acetophenone derivatives, for example α-hydroxycycloalkylphenyl ketone or 2-hydroxy-2- methyl-1-phenyl-propanone, dialkoxyacetophenones, α-hydroxy- or α-amino-aceto- phenones, for example (4-methylthiobenzoyl)-1-methyl-1-morpholino-ethane, (4-morpholino- benzoyl)-1-benzyl-1-dimethylamino-propane, (4-methylthiobenzoyl)-1-methyl-1-morpholino- ethane, (4-morpholino-benzoyl)-1-(4-methyl-benzyl)-1-dimethylamino-propane, 4-aroyl-1 ,3- dioxolanes, benzoin alkyl ethers and benzil ketals, e.g. benzil dimethyl ketal, phenylglyoxalates and derivatives thereof, dimeric phenylglyoxalates, monoacylphosphine oxides, for example (2,4,6-trimethylbenzoyI)-phenyl-phosphine oxide, bisacylphosphine oxides, for example bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethyl-pent-1-yl)phosphine oxide, bis(2,4,6- trimethylbenzoyl)-phenyl-phosphine oxide or bis(2,4,6-trimethylbenzoyl)-(2,4-dipentyl- oxyphenyl)phosphine oxide, trisacylphosphine oxides, ferrocenium compounds or titano- cenes, for example dicyclopentadienyl-bis(2,6-difluoro-3-pyrrolo-phenyl)-titanium and borate salts.
Further examples of suitable photoinitiators are the compounds of formulae V, VI, VII, VIII, IX, X and XI described hereinbelore.
As coinitiators there come into consideration, for example, sensitisers which shift or broaden the spectral sensitivity and thus bring about an acceleration of the photopolymerisation. They are especially aromatic carbonyl compounds, for example benzophenone, thioxanthone, especially isopropyl thioxanthone, anthraquinone and 3- acylcoumarin derivatives, terphenyls, styryl ketones, and also 3-(aroylmethylene)- thiazolines, camphor quinone, and also eosine, rhodamine and erythrosine dyes. Amines, for example, can also come into consideration as photosensitisers when the photoinitiator layer grafted on according to the invention consists of a benzophenone or benzophenone derivative. Further examples of photosensitisers are 1. Thioxanthones
Thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-dodecylthioxanthone, 2,4- diethylthioxanthone, 2,4-dimethylthioxanthone, 1-methoxycarbonylthioxanthone, 2-ethoxy- carbonylthioxanthone, 3-(2-methoxyethoxycarbonyl)-thioxanthone, 4-butoxycarbonylthio- xanthone, 3-butoxycarbonyl-7-methylthioxanthone, 1-cyano-3-chlorothioxanthone, 1-ethoxy- carbonyl-3-chlorothioxanthone, 1 -ethoxycarbonyl-3-ethoxythioxanthone, 1 -ethoxycarbonyl- 3-aminothioxanthone, 1 -ethoxycarbonyl-3-phenylsulfurylthioxanthone, 3,4-di[2-(2-methoxy- ethoxy)ethoxycarbonyl]thioxanthone, 1 -ethoxycarbonyl-3-(1-methyl-1-morpholinoethyl)-thio- xanthone, 2-methyl-6-dimethoxymethyl-thioxanthone, 2-methyl-6-(1 ,1-dimethoxybenzyl)- thioxanthone, 2-morpholiπomethylthioxaπthone, 2-methyI-6-morpholinomethylthioxanthone, N-allylthioxanthone-3,4-dicarboximide, N-octylthioxanthone-3,4-dicarboximide, N-(1 , 1 ,3,3- tetramethylbutyl)-thioxanthone-3,4-dicarboximide, 1 -phenoxythioxanthone, 6-ethoxy- carbonyl-2-methoxythioxanthone, 6-ethoxycarbonyl-2-methylthioxanthone, thioxanthone-2- polyethylene glycol ester, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthon-2-yloxy)-N,N,N- trimethyl-1-propanaminium chloride;
2. Benzophenones
Benzophenone, 4-phenylbenzophenone, 4-methoxybenzophenone, 4,4'-dimethoxybenzo- phenone, 4,4'-dimethylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dimethylamino- benzophenone, 4,4'-diethylaminobenzophenone, 4-methylbenzophenone, 3-methyl-4'- phenylbenzophenone, 2,4,6-trimethylbenzophenone, 2,4,6-trimethyl-4'-phenyl-benzo- phenone, 4-(4-methylthiophenyl)-benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, methyl 2-benzoylbenzoate, 4-(2-hydroxyethylthio)-benzophenone, 4-(4-tolylthio)benzo- phenone, 4-benzoyl-N,N,N-trimethylbenzenemethanaminium chloride, 2-hydroxy-3-(4- benzoylphenoxy)-N,N,N-trimethyl-1-propanaminium chloride monohydrate, 4-(13-acryloyl- 1 ,4,7,10,13-pentaoxatridecyl)-benzoρhenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-prop- enyl)oxy]ethyl-benzenemethanaminium chloride;
3. 3-Acylcoumarins
3-Benzoylcoumarin, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-5,7-di(propoxy)coumarin, 3- benzoyl-6,8-dichlorocoumarin, 3-benzoyl-6-chlorocoumarin, 3,3'-carbonyl-bis[5,7-di(prop- oxy)coumarin], 3,3'-carbonyl-bis(7-methoxycoumarin), 3,3'-carbonyl-bis(7-diethylamino- coumarin), 3-isobutyroylcoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-5,7-di- ethoxycoumarin, 3-benzoyl-5,7-dibutoxycoumarin, 3-benzoyl-5,7-di(methoxyethoxy)-couma- rin, 3-benzoyl-5,7-di(allyloxy)coumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoyl-7- diethylaminocoumarin, 3-isobutyroyl-7-dimethylaminocoumarin, 5,7-dimethoxy-3-(1-naph- thoyl)-coumarin, 5,7-dimethoxy-3-(1-naphthoyl)-coumarin, 3-benzoyIbenzo[f]coumarin, 7- diethylamino-3-thienoylcoumarin, 3-(4-cyanobenzoyl)-5,7-dimethoxycoumarin; 4. 3-(Aroylmethylene)-thiazolines
3-Methyl-2-benzoylmethylene-β-naphthothiazoline, 3-methyl-2-benzoylmethylene- benzothiazoline, 3-ethyl-2-propionylmethylene-β-naphthothiazoline; 5. Other carbonyl compounds
Acetophenone, 3-methoxyacetophenone, 4-phenylacetophenone, benzil, 2-acetylnaphth- alene, 2-naphthaldehyde, 9,10-anthraquinone, 9-fluorenone, dibenzosuberone, xanthone, 2,5-bis(4-diethylaminobenzylidene)cyclopentanone, α-(para-dimethylaminobenzylidene)- ketones, such as 2-(4-dimethylamino-benzylidene)-indan-1-one or 3-(4-dimethylamino- phenyl)-1-indan-5-yl-propenone, 3-phenylthiophthalimide, N-methyl-3,5-di(ethylthio)phthal- imide, N-methyl-3,5-di(ethylthio)phthalimide.
In addition to those additives it is also possible for the radiation-curable composition to comprise further additives, especially light stabilisers. The nature and amount of such additional additives is governed by the intended use of the coating in question and will be familiar to the person skilled in the art.
The compositions may also be pigmented when a suitable photoinitiator is chosen, it being possible for coloured pigments as well as white pigments to be used.
The compositions can be applied in layer thicknesses of from about 0.1 μm to about 1000 μm, especially about from 1 μm to 100 μm. In the range of low layer thicknesses < 50 μm, pigmented compositions e.g. are also referred to as printing inks.
As light stabilisers it is possible to add UV absorbers, e.g. those of the hydroxyphenyl- benzotriazole, hydroxyphenylbenzophenone, oxalic acid amide or hydroxyphenyl-s-triazine type. Such compounds can be used singly or in the form of mixtures, with or without the use of sterically hindered amines (HALS). Examples of such UV absorbers and light stabilisers are
1. 2-(2'-Hvdroxyphenyl)-benzotriazoles, e.g. 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, 2- (3',5'-di-tert-butyl-2'-hydroxyphenyl)-benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl)-benzo- triazole, 2-(2'-hydroxy-5'-(1,1 ,3,3-tetramethylbutyl)-phenyl)-benzotriazole, 2-(3',5'-di-tert- butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5- chlorobenzotriazole, 2-(3'-sec-butyl-5,-tert-butyl-2'-hydroxyphenyl)-benzotriazole, 2-(2'-hyd- roxy-4'-octyloxyphenyl)-benzotriazoIe, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)-benzotriazole, 2-(3',5'-bis(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, mixture of 2-(3'-tert-butyl-2'- hydroxy-5'-(2-octyloxycarbonylethyI)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-5'-[2-(2- ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazoIe, 2-(3'-tert-butyl-2'-hyd- roxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'- (2-methoxycarbonylethyl)phenyl)-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5,-(2-octyloxycar- bonylethyl)phenyl)-benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'- hydroxyphenyl)-benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methyIphenyl)-benzotriazole and 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)-phenyl-benzotriazole, 2,2'-methyl- ene-bis[4-(1 , 1 ,3,3-tetramethylbutyl)-6-benzotriazol-2-yl-phenol]; transesterification product of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-benzotriazole with polyethylene glycol 300; [R-CH2CH2-COO(CH2)3]2- wherein R = S'-tert-butyW-hydroxy-S'- 2H-benzotriazol-2-yl-phenyl .
2. 2-Hvdroxybenzophenones, e.g. the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4- dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy or 2'-hydroxy-4,4'-dimethoxy derivative.
3. Esters of unsubstituted or substituted benzoic acids, e.g. 4-tert-butyl-ρhenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)- resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, 3,5-di-tert-butyl-4-hydroxy- benzoic acid octadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2-methyl-4,6-di-tert- butylphenyl ester.
4. Acrylates, e.g. α-cyano-β,β-diphenylacrylic acid ethyl ester or isooctyl ester, α-methoxy- carbonylcinnamic acid methyl ester, α-cyano-β-methyl-p-methoxycinnamic acid methyl ester or butyl ester, α-methoxycarbonyl-p-methoxycinnamic acid methyl ester, N-(β-methoxy- carboπyl-β-cyanovinyl)-2-methyl-indoline.
5. Stericallv hindered amines, e.g. bis(2,2,6,6-tetramethylpiperidyl) sebacate, bis(2, 2,6,6- tetramethylpiperidyl) succinate, bis(1, 2,2,6, 6-pentamethylpiperidyl) sebacate, n-butyl-3,5-di- tert-butyl-4-hydroxybenzylmalonic acid bis(1 ,2,2,6,6-pentamethylpiperidyl) ester, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1 ,3,5-s-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotri- acetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1 ,2,3,4-butanetetraoate, 1 ,1'-(1 ,2-ethane- diyl)bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyl- oxy-2,2,6,6-tetramethylpiperidine, bis(1 ,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2- hydroxy-3,5-di-tert-butylbenzyI) alonate, 3-n-octyl-7,7,9,9-tetramethyl-1 ,3,8-triazaspiro- [4.5]decane-2,4-dione, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis(1-octyloxy- 2,2,6,6-tetramethylpiperidyl) succinate, condensation product of N,N'-bis(2,2,6,6- tetramethyl-4-piρeridyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1 ,3,5-triazine, condensation product of 2-chloro-4,6-di(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1 ,3,5- triazine and 1 ,2-bis(3-aminopropylamino)ethane, condensation product of 2-chloro-4,6-di(4- n-butylamino-1 ,2,2,6,6-pentamethylpiperidyI)-1 ,3,5-triazine and 1 ,2-bis(3- aminopropylamino)ethane, 8-acetyl-3-dodecyI-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]- decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,
3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione.
6. Oxalic acid diamides, e.g. 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy- 5,5'-di-tert-butyl oxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyl oxanilide, 2-ethoxy-2'-ethyl oxanilide, N,N'-bis(3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyl oxanilide and a mixture thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyl oxanilide, mixtures of o- and p- methoxy- and also of o- and p-ethoxy-di-substituted oxanilides.
7. 2-(2-HydroxyphenvD-1 ,3,5-triazines, e.g. 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1 ,3,5- triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-(2,4-di- hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxy- phenyl)-6-(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4- methylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)- 1 ,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl- phenyl)-1 ,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyIoxy)phenyl]-4,6-bis(2,4- dimethylphenyl)-1,3,5-triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropyl)oxy-2-hydroxy- phenyl]-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine.
In addition to the light stabilisers mentioned above, other stabilisers, for example, such as phosphites or phosphonites, are also suitable.
8. Phosphites and phosphonites, e.g. triphenyl phosphite, diphenylalkyl phosphites, phenyl- dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl-pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecylpenta- erythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert- butyl-4-methylphenyl)pentaerythritol diphosphite, bis-isodecyloxy-pentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-tert- butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert- butylpheπyl)-4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H- dibenzo[d,g]-1,3,2-dioxaphosphocine, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo- [d,g]-1 ,3,2-dioxaρhosphocine, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, bis(2,4- di-tert-butyl-6-methyIphenyl)ethyl phosphite.
Depending upon the field of use, it is also possible to use additives customary in the art, e.g. antistatics, flow improvers and adhesion promoters.
Compositions applied in process step d1) or d2) are, for example, pigmented or unpigmented surface coatings, inks, ink-jet inks; printing inks, for example screen printing inks, offset printing inks, flexographic printing inks; or overprint varnishes; or primers; or printing plates, offset printing plates; powder coatings, adhesives, pressure -sensitive adhesives, e.g. including hot-melt pressure-sensitive adhesives, or repair coatings, repair varnishes or repair putty compositions.
The compositions used in process step d1) need not necessarily comprise a photoinitiator — for example they may be customary electron-beam-curable compositions (without photoinitiator) known to the person skilled in the art.
The substrates pretreated using steps a) - c) in accordance with the process of the invention can, as already mentioned, be coated in a further step d1) with customary photocurable compositions and cured with UVΛ IS or an electron beam or d2) can be provided with a customary coating, such coatings being dried, for example, in air or thermally. The drying can be effected, for example, also by absorption, for example by penetration into the substrate.
The coating used in process step d2) is preferably a printing ink.
Such printing inks are known to the person skilled in the art, are used widely in the art and are described in the literature.
They are, for example, pigmented printing inks and printing inks coloured with dyes.
A printing ink is, for example, a liquid or paste-form dispersion that comprises colorants
(pigments or dyes), binders and also optionally solvents and/or optionally water and additives. In a liquid printing ink, the binder and, if applicable, the additives are generally dissolved in a solvent. Customary viscosities in the Brookfield viscometer are, for example, from 20 to 5000 mPa-s, for example from 20 to 1000 Pa^s, for liquid printing inks. For paste-form printing inks, the values range, for example, from 1 to 100 Pa-s, preferably from 5 to 50 Pa'S. The person skilled in the art will be familiar with the ingredients and compositions of printing inks.
Suitable pigments, like the printing ink formulations customary in the art, are generally known and widely described.
Printing inks comprise pigments advantageously in a concentration of, for example, from 0.01 to 40 % by weight, preferably from 1 to 25 % by weight, especially from 5 to 10 % by weight, based on the total weight of the printing ink.
The printing inks can be used, for example, for intaglio printing, flexographic printing, screen printing, offset printing, lithography or continuous or dropwise ink-jet printing on material pretreated in accordance with the process of the invention using generally known formulations, for example in publishing, packaging or shipping, in logistics, in advertising, in security printing or in the field of office equipment.
Suitable printing inks are both solvent-based printing inks and water-based printing inks. Of interest are, for example, printing inks based on aqueous acrylate. Such inks are to be understood as including polymers or copolymers that are obtained by polymerisation of at ffH*,? fi 0 / least one monomer containing a group — c-c-o— or — C-C-N- and that are dissolved in water or a water-containing organic solvent. Suitable organic solvents are water-miscible solvents customarily used by the person skilled in the art, for example alcohols, such as methanol, ethanol and isomers of propanol, butanol and pentanol, ethylene glycol and ethers thereof, such as ethylene glycol methyl ether and ethylene glycol ethyl ether, and ketones, such as acetone, ethyl methyl ketone or cyclo, for example isopropanol. Water and alcohols are preferred.
Suitable printing inks comprise, for example, as binder primarily an acrylate polymer or copolymer and the solvent is selected, for example, from the group consisting of water,
Ci-Csalcohols, ethylene glycol, 2-(d-C5alkoxy)-ethanoI, acetone, ethyl methyl ketone and any mixtures thereof.
In addition to the binder, the printing inks may also comprise customary additives known to the person skilled in the art in customary concentrations.
For intaglio or flexographic printing, a printing ink is usually prepared by dilution of a printing ink concentrate and can then be used in accordance with methods known perse.
The printing inks may, for example, also comprise alkyd systems that dry oxidatively. The printing inks are dried in a known manner customary in the art, optionally with heating of the coating.
A suitable aqueous printing ink composition comprises, for example, a pigment or a combination of pigments, a dispersant and a binder.
Dispersants that come into consideration include, for example, customary dispersants, such as water-soluble dispersants based on one or more arylsulfonic acid/formaldehyde condensation products or on one or more water-soluble oxalkylated phenols, non-ionic dispersants or polymeric acids.
The arylsulfonic acid/formaldehyde condensation products are obtainable, for example, by sulfonation of aromatic compounds, such as naphthalene itself or naphthalene-containing mixtures, and subsequent condensation of the resulting arylsulfonic acids with formaldehyde. Such dispersants are known and are described, for example, in US-A- 5 186 846 und DE-A-19727 767. Suitable oxalkylated phenols are likewise known and are described, for example, in US-A-4218 218 und DE-A-197 27 767. Suitable non-ionic dispersants are, for example, alkylene oxide adducts, polymerisation products of vinylpyrrolidone, vinyl acetate or vinyl alcohol and co- or ter-polymers of vinyl pyrrolidone with vinyl acetate and/or vinyl alcohol.
It is also possible, for example, to use polymeric acids which act both as dispersants and as binders.
Examples of suitable binder components that may be mentioned include acrylate-group- containing, vinyl-group-containing and/or epoxy-group-containing monomers, prepolymers and polymers and mixtures thereof. Further examples are melamine acrylates and silicone acrylates. The acrylate compounds may also be non-ionically modified (e.g. provided with amino groups) or ionically modified (e.g. provided with acid groups or ammonium groups) and used in the form of aqueous dispersions or emulsions (e.g. EP-A-704 469, EP-A-12 339). Furthermore, in order to obtain the desired viscosity the solventless acrylate polymers can be mixed with so-called reactive diluents, for example vinyl- group-containing monomers. Further suitable binder components are epoxy-group- containing compounds.
The printing ink compositions may also comprise as additional component, for example, an agent having a water-retaining action (humectant), e.g. polyhydric alcohols, polyalkylene glycols, which renders the compositions especially suitable for ink-jet printing. It will be understood that the printing inks may comprise further auxiliaries, such as are customary especially for (aqueous) ink-jet inks and in the printing and coating industries, for example preservatives (such as glutardialdehyde and/or tetramethylolacetyleneurea, anti- oxidants, degassers/defoamers, viscosity regulators, flow improvers, anti-settling agents, gloss improvers, lubricants, adhesion promoters, anti-skin agents, matting agents, emulsifiers, stabilisers, hydrophobic agents, light stabilisers, handle improvers and antistatics. When such agents are present in the compositions, their total amount is generally < 1 % by weight, based on the weight of the preparation.
Printing inks suitable in process step d2) also include, for example, those comprising a dye (with a total content of dyes of e.g. from 1 to 35 % by weight, based on the total weight of the ink).
Dyes suitable for colouring such printing inks are known to the person skilled in the art and are widely available commercially, e.g. from Ciba Spezialitatenchemie AG, Basel. Such printing inks may comprise organic solvents, e.g. water-miscible organic solvents, for example Cι-C4alcohols, amides, ketones or ketone alcohols, ethers, nitrogen-containing heterocyclic compounds, polyalkylene glycols, C2-Cealkylene glycols and thioglycols, further polyols, e.g. glycerol and d-dalkyl ethers of polyhydric alcohols, usually in an amount of from 2 to 30 % by weight, based on the total weight of the printing ink. The printing inks may also, for example, comprise solubilisers, e.g. ε-caprolactam. The printing inks may, inter alia for the purpose of adjusting the viscosity, comprise thickeners of natural or synthetic origin. Examples of thickeners include commercially available alginate thickeners, starch ethers or locust bean flour ethers. The printing inks comprise such thickeners e.g. in an amount of from 0.01 to 2 % by weight, based on the total weight of the printing ink.
It is also possible for the printing inks to comprise buffer substances, for example borax, borate, phosphate, polyphosphate or citrate, in amounts of e.g. from 0.1 to 3 % by weight, in order to establish a pH value of e.g. from 4 to 9, especially from 5 to 8.5. As further additives, such printing inks may comprise surfactants or humectants. Surfactants that come into consideration include commercially available anionic and non- ionic surfactants. Humectants that come into consideration include, for example, urea or a mixture of sodium lactate (advantageously in the form of a 50 to 60 % aqueous solution) and glycerol and/or propylene glycol in amounts of e.g. from 0.1 to 30 % by weight, especially from 2 to 30 % by weight, in the printing inks.
Furthermore, the printing inks may also comprise customary additives, for example foam- reducing agents or especially substances that inhibit the growth of fungi and/or bacteria. Such additives are usually used in amounts of from 0.01 to 1 % by weight, based on the total weight of the printing ink.
The printing inks may also be prepared in customary manner by mixing the individual components together, for example in the desired amount of water.
As already mentioned, depending upon the nature of the use, it may be necessary for e.g. the viscosity or other physical properties of the printing ink, especially those properties which influence the affinity of the printing ink for the substrate in question, to be adapted accordingly.
The printing inks are also suitable, for example, for use in recording systems of the kind in which a printing ink is expressed from a small opening in the form of droplets which are directed towards a substrate on which an image is formed. Suitable substrates are, for example, textile fibre materials, paper, plastics or aluminium foils pretreated by the process according to the invention. Suitable recording systems are e.g. commercially available ink- jet printers. Preference is given to printing processes in which aqueous printing inks are used.
When, according to process step d3), a metal, semi-metal, metal oxide or semi-metal oxide layer is applied as the strongly adhering layer, the following metals are preferred: gold, silver, platinum, palladium, chromium, molybdenum, tin, aluminium or copper, especially aluminium and copper. The following semi-metal and metal oxides are of interest: aluminium oxide, chromium oxide, iron oxide, copper oxide and silicon oxide.
The metals, semi-metal or metal oxides are vaporised under vacuum conditions and deposited onto the substrate precoated with photoinitiator.
The crucible temperatures for the vaporisation process depend upon the metal or oxide being vaporised and are, for example, 300-2000°C, especially 800-1800°C.
The metal-coated substrates are suitable, for example, for flexible circuit board applications, diffusion barrier layers, electromagnetic shields or they form decorative elements. The process according to the invention can be carried out within a wide pressure range, the discharge characteristics shifting as the pressure increases from a pure low-temperature plasma towards a corona discharge and finally changing into a pure corona discharge at an atmospheric pressure of about 1000-1100 mbar.
The process is preferably carried out at a process pressure of from 10"β mbar up to atmospheric pressure (1013 mbar), especially in the range of from 10"4 to 10"2 mbar as a plasma process and at atmospheric pressure as a corona process. The flame treatment is usually carried out at atmospheric pressure.
The process is preferably carried out using as the plasma gas an inert gas or a mixture of an inert gas with a reactive gas.
When a corona discharge is used, air, C02 and/or nitrogen are preferably used as the gas. It is especially preferred to use air, H2, C02, He, Ar, Kr, Xe, N2, 02 or H20 singly or in the form of a mixture.
The photoinitiator layer deposited preferably has a thickness ranging from e.g. a mono- molecular layer up to 500 nm, especially from 5 nm to 200 nm.
The plasma- or corona-treatment of the inorganic or organic substrate a) preferably takes place for from 1 ms to 300 s, especially from 10 ms to 200 s.
In principle, it is advantageous to apply the photoinitiator as quickly as possible after the plasma-, corona- or flame-pretreatment, but for many purposes it may also be acceptable to carry out reaction step b) after a time delay. It is preferable, however, to carry out process step b) immediately after process step a) or within 24 hours after process step a). Of interest is a process wherein process step c) is carried out immediately after process step b) or within 24 hours after process step b).
The pretreated and photoinitiator-coated substrate can be subjected to process step d) [that is to say d1 ) or d2)] immediately after the coating and drying in accordance with process steps a), b) and c) or it can be stored in the pretreated form. The photoinitiator of formula I, II, HI or IV, or where applicable the mixture of a plurality of photoinitiators and/or coinitiators, is applied to the corona-, plasma- or flame-pretreated substrate, for example, in pure form, that is to say without further additives, or in combination with a monomer or oligomer, or dissolved in a solvent. The initiator, or the initiator mixture, can also e.g. be in molten form. The initiator, or the initiator mixture, can also, for example, be dispersed, suspended or emulsified in water, a dispersant being added as necessary. Of course, it is also possible to use any mixture of the above- mentioned components, photoinitiator, monomer, oligomer, solvent, water. Suitable dispersants, e.g. any surface-active compounds, preferably anionic and non-ionic surfactants, and also polymeric dispersants, are usually known to the person skilled in the art and are described, for example, in US 4965 294 and US 5 168 087. Suitable solvents are in principle any substances in which the photoinitiator, or the photoinitiators, can be converted into a state suitable for application, whether in the form of a solution or in the form of a suspension or emulsion. Suitable solvents are, for example, alcohols, such as ethanol, propanol, isopropanol, butanol, ethylene glycol efc., ketones, such as acetone, methyl ethyl ketone, acetonitrile, aromatic hydrocarbons, such as toluene and xylene, esters and aldehydes, such as ethyl acetate, ethyl formate, aliphatic hydrocarbons, e.g. petroleum ether, pentane, hexane, cyclohexane, halogenated hydrocarbons, such as dichloromethane, choroform, or alternatively oils, natural oils, castor oil, vegetable oil efc., and also synthetic oils. This description is on no account exhaustive and is given merely by way of example. Alcohols, water and esters are preferred.
Suitable monomers and oligomers are, for example, those described above in connection with the photocurable composition (process step d1).
The invention therefore relates also to a process wherein the photoinitiators of formula I, II, III and/or IV or mixtures thereof with monomers or oligomers are used in combination with one or more liquids (such as solvents or water) in the form of solutions, suspensions and emulsions.
Also of interest is a process wherein the photoinitiator used in process step b) or the mixture of photoinitiators is used in molten form. After the plasma-, corona- or flame-pretreatment, it is therefore possible in process step b) to apply to the pretreated substrate, for example, 0.1-15 %, e.g. 0.1-5 %, of a photoinitiator of formula I, II, III and/or IV having an unsaturated group and e.g. 0.5-10 % of a monomer, such as an acrylate, methacrylate, vinyl ether efc..
The application of the photoinitiators, or mixtures thereof with one another or with monomers or oligomers, in the form of melts, solutions, dispersions, suspensions or emulsions, can be carried out in various ways. Application can be effected by immersion, spraying, coating, brush application, knife application, roller application, printing, spin- coating and pouring. In the case of mixtures of photoinitiators with one another and with coinitiators and sensitisers, all possible mixing ratios can be used. When only one photoinitiator or photoinitiator mixture is to be applied to the pretreated substrate, the concentration of those initiators is, of course, 100 %.
When the photoinitiators are applied in the form of mixtures with monomers or/and solvents or/and water in the form of liquids, solutions, emulsions or suspensions, they are used, for example, in concentrations of from 0.01 to 99.9 %, or 0.01-80 %, e.g. 0.1-50 %, or 10-90 %, based on the solution being applied. The liquids comprising the photoinitiator may, in addition, contain e.g. further substances, such as defoamers, emulsifiers, surfactants, anti- fouling agents, wetting agents and other additives customarily used in the industry, especially the coating and paint industries.
Many possible methods of drying coatings are known and they can all be used in the claimed process. For example, it is possible to use hot gases, IR radiators, microwave and radio frequency radiators, ovens and heated rollers. Drying can also be effected, for example, by absorption, e.g. penetration into the substrate. This relates especially to the drying in process step c), but applies also to the drying carried out in process step d2). Drying can take place, for example, at temperatures of from 0°C to 300°C, for example from 20°C to 200°C.
The irradiation of the coating in order to fix the photoinitiator in process step c) (and also to cure the formulation in process step d1) can be carried out, as already mentioned above, using any sources that emit electromagnetic waves of wavelengths that can be absorbed by the photoinitiators used. Such sources are generally light sources that emit light in the range from 200 nm to 700 nm. It may also be possible to use electron beams. In addition to customary radiators and lamps it is also possible to use lasers and LEDs (Light Emitting Diodes). The whole area of the coating or parts thereof may be irradiated. Partial irradiation is of advantage when only certain regions are to be rendered adherent. Irradiation can also be carried out using electron beams.
The drying and/or irradiation can be carried out under air or under inert gas. Nitrogen gas comes into consideration as inert gas, but other inert gases, such as C02 or argon, helium efc. or mixtures thereof, can also be used. Suitable systems and apparatus are known to the person skilled in the art and are commercially available.
The invention relates also to the use of photoinitiators of formulae I, II, III and IV and photoinitiator systems comprising at least one compound of formula I, II, III or IV in combination with a further photoinitiator, e.g. a photoinitiator of formula V, VI, VII, VIII, IX, X and/or XI, in the process according to the invention.
The invention relates also to strongly adherent coatings obtainable in accordance with the process described above.
Such strongly adherent coatings are important not only as protective layers or coverings, which may additionally be pigmented, but also for image-forming coatings, for example in resist and printing plate technology. In the case of image-forming processes, the irradiation can be effected through a mask or by writing using moving laser beams (Laser Direct
Imaging - LDI). Such partial irradiation can be followed by a development or washing step in which portions of the applied coating are removed by means of solvents and/or water or mechanically.
When the process according to the invention is used in the production of image-forming coatings (imaging), for example in the production of printing plates or electronic printed circuit boards, the image-forming step can be carried out either in process step c) or in process step d).
In step d), depending upon the coating formulation used, the image-forming step may be a crosslinking reaction or alternatively a reaction in which the solubility of the formulation is altered.
The invention therefore relates also to a process wherein portions of the photoinitiators, or mixtures thereof with monomers and/or oligomers, applied in process step b) that have not been crosslinked after irradiation in process step c) are removed by treatment with a solvent and/or water and/or mechanically, and to a process wherein after irradiation in process step d1) portions of the coating are removed by treatment with a solvent and/or water and/or mechanically.
It is also possible to use image-forming processes either in one of the two process steps c) and d1) or in both steps c) and d1) in succession.
The process according to the invention proves to be especially advantageous in respect of improving the adhesion of UV-curing coatings, printing inks, adhesives, on plastics, especially in respect of the adhesion of pigmented coatings. It is possible, for example, to produce pigmented and thick strongly adherent coating layers, for example also with black printing inks which exhibit high absorption.
In addition, the process according to the invention can be used to improve the adhesion of structurable metal coatings on organic and inorganic substrates.
The following Examples further illustrate the invention. As in the remainder of the description and in the claims, parts and percentages relate to weight, unless otherwise indicated. Where alkyl or alkoxy radicals having more than three carbon atoms are mentioned without any reference to their isomeric form, the data relate to the respective n-isomer.
Example 1: Preparation of lithium (2,4,6-trimethylbenzoyl)-phenyl-phosphine
Figure imgf000052_0001
Under argon and with the exclusion of moisture, 14.0 g of lithium (2.0 mol) are introduced at room temperature into 250 ml of tetrahydrofuran. At 20-25°C, with stirring, 44.8 g (0.25 mol) of dichlorophenylphosphine are added dropwise. Then 1.25 g of naphthalene are added and after 4 hours' stirring the red solution is filtered, with the exclusion of moisture and under argon as protective gas, through a frit (G2 porosity) into a three-necked round- bottomed flask. At room temperature, with stirring and cooling, 47.2 g (0.258 mol) of 2,4,6- trimethylbenzoyl chloride are added dropwise within a period of 30 minutes. After 2 hours' stirring, the title compound is obtained in the form of a red solution in tetrahydrofuran. (Shift in the 31P-NMR: 98.4 ppm) Example 2: Preparation of 2,4,6-trimethylbenzoyl-allyl-phenyl-phosphine oxide
Figure imgf000053_0001
At 20-30°C, 6.05 g (0.05 mol) of bromide are added dropwise within a period of 20 min to 35 ml (0.022 mol) of the solution as obtained in Example 1. After 2 hours' stirring, the orange reaction suspension is concentrated using a rotary evaporator. The residue is taken up in 50 ml of toluene, and 5.7 g (0.05 mol) of hydrogen peroxide 30 % are added. After 2 hours' stirring at 20-30°C, the reaction is complete. The reaction emulsion is poured into water and washed with aqueous saturated sodium hydrogen carbonate solution, then dried over magnesium sulfate and filtered. The filtrate is concentrated using a rotary evaporator. The residue is purified over silica gel and dried under a high vacuum. The title compound is obtained in the form of a yellowish oil. 31P-NMR 26.60 ppm; 1H-NMR (ppm): 7.36-7.78 (m), 6.69 (s), 5.74-5.78 (m), 5.12-5.23 (m), 3.0-3.30 (m), 2.18 (s) and 1.97 (s), measured in CDCI3
Examples 3-5:
The compounds of Examples 3-5 are prepared analogously to the method described in
Example 2, the compound according to Example 1 being reacted with the respective starting material indicated in the following Table. The compounds and their physical data are shown in the following Table 1.
Table 1
Figure imgf000053_0002
Figure imgf000054_0003
Example 6: Preparation of lithium (2,4,6-trimethylbenzoyl)-isobutyl-phosphine
Figure imgf000054_0001
34.4 ml (0.055 mol, +10 %) of butyl lithium 1.6M are slowly added dropwise at 0-10°C to 4.5 g (0.025 mol) of isobutylphenylphosphine (50 % solution in toluene) in 30 ml of tetrahydrofuran. Then, with the temperature unchanged, 4.6 g (0.025 mol) of 2,4,6-trimethyl- benzoyl chloride are added dropwise. After heating to room temperature, the title compound is obtained in the form of an orange suspension (31P-NMR: 50 ppm).
Example 7: Preparation of lithium (2,4,6-trimethylbenzoyl)-(2,4,4-trimethylpentyl)-phosphine
Figure imgf000054_0002
The compound is obtained analogously to the method described in Example 6 by replacing isobutylphenylphosphine by 2,4,4-trimethylpentylphosphine. (31P-NMR: 49.2 ppm). Example 8: Preparation of 2,4,6-trimethylbenzoyl-isobutyl-allyl-ρhosphine oxide
Figure imgf000055_0001
3.03 g (0.025 mol) of allyl bromide are slowly added dropwise at room temperature to the suspension of lithium (2,4,6-trimethylbenzoyl)-isobutyl-phosphine obtained according to Example 6. After 1 hour's stirring at room temperature, the orange reaction suspension is concentrated using a rotary evaporator. The residue is taken up in 50 ml of toluene, and 4.2 g (0.0375 mol) of hydrogen peroxide 30 % are added. After 2 hour's stirring at 20-30°C, the reaction is complete. The reaction emulsion is poured into water and washed with aqueous saturated sodium hydrogen carbonate solution, then dried over magnesium sulfate and filtered. The filtrate is concentrated using a rotary evaporator. The residue is purified over silica gel and dried under a high vacuum. The title compound is obtained in the form of a yellow viscous oil. 31 P-NMR: 39.2 ppm; 1H-NMR (ppm): 1.04 d; 1.07 d; 1.83 m; 2.19 m; 2.28 s; 2.31 s; 2.84 m; 5.21 m; 5.27 d; 5.83 m; 6.86 s, measured in CDCI3.
Example 9: Preparation of 2,4,6-trimethylbenzoyl-(2,4,4-trimethylρentyl)-allyl-phosphine oxide
Figure imgf000055_0002
The compound of Example 9 is obtained analogously to the method described in Example 8 using the compound described in Example 7 and ally] bromide as starting materials. 31 P-NMR: 39.06 ppm; 1H-NMR (measured irt CDCI3; ppm): 0.90 d; 1.11-1.15 t; 1.20-1.39 m; 1.72-2.14 m; 2.28-2.31 d; 2.76-2.88 m; 5.20-5.27 m; 5.77-5.90 ; 6.86 s.
Example 10:
Preparation of phenyl-phosphonous acid di-2-allyloxyethyl ester
Figure imgf000055_0003
40 g (0.22 mol) of dichlorophenylphosphine, 56.87 g (0.47 mol) of N,N-dimethyIaniline and 39.38 g (0.45 mol) 2-allyloxyethanol are introduced into 150 ml of diethyl ether and boiled at reflux overnight. After cooling to room temperature, filtration is carried out and the filtrate is purified by chromatography. The title compound is obtained in the form of a colourless liquid.
Examples 11 and 12:
The compounds of Examples 11 and 12 are obtained analogously to the method described in Example 10. The compounds are shown in Table 2.
Figure imgf000056_0002
Example 13: Preparation of a mixture of phenyl-(2,4,6-trimethylbenzoyl)-phosphinic acid 2- vinyloxy-ethyl ester and phenyl-(2,4,6-trimethylbenzoyl)-phosphonic acid vinyl ester
Figure imgf000056_0001
Under argon, 40.82 g ( .22 mol) of 2,4,6-trimethylbenz c acid chloride dissolved in 50 ml of toluene are added dropwise at 80°C within a period of 30 minutes to 40 g (0.22 mol) of phenyl-phosphonous acid di-2-vinyloxy-ethyl ester in 150 ml of toluene. The reaction solution is stirred at 80°C for 18 hours, cooled and poured into aqueous K2C03 solution. The organic phase is separated off and washed twice with water, dried over sodium sulfate and concentrated by evaporation using a rotary evaporator. The crude product is chromato- graphed on silica gel and the product is isolated as a mixture consisting of phenyl-(2,4,6- trimethylbenzoyl)phosphinic acid 2-vinyloxy-ethyl ester and phenyl-(2,4,6-trimethyl- benzoyl)phosphonic acid' vinyl ester in a ratio of 4:1 (according to 1H-NMR) in the form of a yellowish oil. 31P-NMR of the mixture: 19.45 and 19.60 ppm; 1H-NMR of the mixture, measured in CDCI3 in ppm: 7.82-7.88 (m), 7.58-7.61 (m), 7.45-7.52 (m), 7.85 (s), 6.81 (s), 6.36-6.43 (dxd), 6.09-6.12 (m), 4.26-4.32 (m), 4.12-4.18 (dxd), 4.00-4.03 (dxd), 3.85-3.88 (t), 2.35 (s), 2.27 (s), 2.15 (s).
Examples 14-15:
The compounds of Examples 14 and 15 are prepared analogously to the method described in Example 10 from 2,4,6-trimethylbenzoic acid chloride and the respective starting material indicated in Table 2. The compounds and the physical data are given in the following Table 3.
Figure imgf000057_0001
Example 16: Adhesion of a blue printing ink
Films of polypropylene (PP Pentaprop) are treated at 5x10"2mbar for about 1 second with an argon/02 plasma (30 sccm:6 seem). The plasma is switched off and the pressure is reduced to 5x10"5mbar. In the plasma chamber there are vaporised in a heatable crucible in one test the photoinitiator from Example 5 at 100°C and, in another instance, the photoinitiator from Example 3 at 85°C for about 2-3 minutes, a layer thickness of about
20 nm being obtained in each case. The thickness is measured by means of a commercially available quartz resonator.
A radiation-curable blue printing ink (UV-Temp 43 Y 000 239, Hostmann Steinberg) is applied to the substrates so pretreated in a layer thickness of about 2 μm. Curing is effected by exposure using a Fusion H lamp (120 W/cm) at a belt speed of 30 m/min. The adhesion properties are tested by crosscutting and tearing off an adhesive tape strip applied to the cured formulation (crosscut test; CC test).
Whereas no adhesion is obtained on a non-pretreated sample, good adhesion is achieved on substrates that have been pretreated with both the photoinitiators used.
Example 17: Adhesion of a blue printing ink
Polypropylene films are pretreated as described in Example 16, the photoinitiator according to Example 5 being used. Prior to application of the printing ink, the treated films are stored for 30 days and then coated with printing ink and tested as described in Example 16. Good adhesion is achieved in this case too.
Example 18: Adhesion of a blue printing ink
Films of polypropylene (PP Pentaprop 11/0000 621 H2, 250 μm, Klδckner Penataplast) are subjected to a corona treatment three times at a speed of 20 m/min and an output of 1000 W and then coated with a solution of 1 % of the initiator from Example 3 and 1 % tris(2-hydroxyethyl)-isocyanurate triacrylate in isopropanol using a 6 μm wire bar. After drying, the films are exposed by means of a Fusion H lamp (120 W/cm) at a belt speed of 15 m/min. An approximately 1-2 μm thick layer of a UV-curable blue offset printing ink (Sicura Plast 770, SICPA) is printed onto the resulting treated films by means of an Orange- Proofer (IGT Testing Systems) at a printing force of 500 N. The layer is cured by means of a Fusion H lamp (120 W/cm) at a belt speed of 15 m/min. Evaluation of the crosscut test for the treated films results in a CC value of 0 (no detachment), whereas a solely corona- treated sample has a CC value of 1 and an untreated film has a CC value of 5 (complete detachment). Example 19:
PP films (Rayoface Polypropylene Film 58 μm, UCB) are subjected to a corona treatment at a speed of 50 m/min and an output of 1000 W and then coated with a solution of 1 % of the initiator of Example 3 and 1 % tris(2-hydroxyethyl)-isocyanurate triacrylate in isopropanol by means of a 6 μm wire bar. After drying, the films are exposed using a Fusion H lamp (120 W/cm) at a belt speed of 15 m/min. An approximately 1-2 μm thick layer of a UV- curable blue offset printing ink (Sicura Plast 770, SICPA) is printed onto the resulting treated films by means of an Orange-Proofer (IGT Testing Systems) at a printing force of 500 N. The layer is cured by means of a Fusion H lamp (120 W/cm) at a belt speed of 15 m/min. The evaluation of the crosscut test for the treated films results in a CC value of 0 (no detachment), whereas a solely corona-treated sample has a CC value of 4-5 and an untreated film has a CC value of 5 (complete detachment).

Claims

What is claimed is:
1. A process for the production of a strongly adherent coating on an inorganic or organic substrate, wherein a) a low-temperature plasma treatment, a corona discharge treatment or a flame treatment is carried out on the inorganic or organic substrate, b) one or more photoinitiators or mixtures of photoinitiators with monomers or/and oligomers, containing at least one ethylenically unsaturated group, or solutions, suspensions or emulsions of the afore-mentioned substances, are applied to the inorganic or organic substrate, and optionally c) using suitable methods those afore-mentioned substances are dried and/or are irradiated with electromagnetic waves, wherein there is used as photoinitiator at least one compound of formula (I), (II), (III) and/or (IV)
IN-L-RG (I)
Figure imgf000060_0001
IN-L-RGr-LHN., (Ill)
IN-L-Rd-Li-RG -Lz-INi (IV), wherein
IN and INι are each independently of the others a monacylphosphine, monoacylphosphine oxide or monoacylphosphine sulfide photoinitiator group;
L, Li and L2 are each independently of the others a single bond or a spacer group; RG is a monovalent radical having at least one ethylenically unsaturated C=C bond; and Gi and RG2 are each independently of the other a divalent radical having at least one ethylenically unsaturated C=C bond.
2. A process for the production of a strongly adherent coating on an inorganic or organic substrate, wherein a) a low-temperature plasma treatment, a corona discharge treatment or a flame treatment is carried out on the inorganic or organic substrate, b) one or more photoinitiators of formula (I), (II), (III) and/or (IV) according to claim 1 or mixtures of such photoinitiators with monomers or/and oligomers, containing at least one ethylenically unsaturated group, or solutions, suspensions or emulsions of the aforementioned substances, are applied to the inorganic or organic substrate, optionally c) using suitable methods those afore-mentioned substances are dried and/or irradiated with electromagnetic waves and either d1) the substrate so precoated with photoinitiator is coated with a composition comprising at least one ethylenically unsaturated monomer or oligomer and the coating is cured by means of UVΛ/IS radiation or an electron beam; or d2) the substrate so precoated with photoinitiator is coated with a printing ink and dried; or d3) a metal, semi-metal, metal oxide or semi-metal oxide is deposited from the gaseous phase onto the substrate so precoated with photoinitiator.
3. A process according to either claim 1 or claim 2, wherein in the compounds of formulae (I), (II), (III) and (IV)
IN and INi are each independently of the other A-G-P— wherein
R
E is O or S; x is 0 or 1 ;
A is , cyclopentyl, cyclohexyl, naphthyl, biphenylyl, anthryl or an O-, S- or N-
Figure imgf000061_0001
containing 5- or 6-membered heterocyclic ring, wherein the radicals cyclopentyl, cyclohexyl, naphthyl, biphenylyl, anthryl or the O-, S- or N-containing 5- or 6-membered heterocyclic ring are unsubstituted or substituted by halogen, C C4alkyl or by d-C4alkoxy;
Ri and R2 are each independently of the other C C2 alkyI, ORn, CF3 or halogen;
R3, R and R5 are each independently of the others hydrogen, Cι-C2 alkyl, ORn or halogen; or two of the radicals Ri, R2, R3, R4 or R5 together are C2-Cι2alkylene which is uninterrupted or interrupted by one or more O, S or NRM;
R is Cι-C24alkyl unsubstituted or substituted by C3-C24cycloalkyl, C3-C24cycloalkenyl, phenyl,
CN, C(0)Rn, C(0)ORn, C(0)N(R14)2, OC(0)Rn, OC(0)ORn, N(R14)C(0)N(Rι4),
OC(0)NRM, N(Ri4)C(0)ORn, halogen, ORn, SRn or by N(Rι2)(Rι3); or R is C2-C24alkyl interrupted one or more times by non-consecutive O or S and unsubstituted or substituted by phenyl, ORn, CN, C(0)Rn, C(0)ORn or by C(0)N(R14)2; or R is C2-C24alkenyl uninterrupted or interrupted one or more times by non-consecutive O and unsubstituted or substituted by ORn or by
Figure imgf000061_0002
or R is C5-C24cycloalkenyl uninterrupted or interrupted one or more times by non-consecutive O, S or NRM and unsubstituted or substituted by ORn or by Cι-Cι2alkyl; or R is C7-C24arylalkyl unsubstituted or substituted at the aryl radical by Cι-d2alkyl or by Cι-Cι2alkoxy; or R is C4-C24cycloalkyl uninterrupted or interrupted one or more times by non-consecutive O, S or NRM and unsubstituted or substituted by ORn or by Ci-Caalkyl;
or R is o / \ , C8-C24arylcycloalkyl or C8-C24arylcycloalkenyl;
R6, R7, R8, R9 and R10 are each independently of the others hydrogen, Cι-C24alkyl unsubstituted or substituted by SRn, N(Rι2)(Rι3), ORn or by phenyl; or R6, R7, R8, R9 and Rι0 are C2-C24alkyl interrupted one or more times by non-consecutive O and unsubstituted or substituted by SRn, N(Rι2)(Rι3), ORn or by phenyl; or R6, R7, R8, R9 and Rι0 are SRn, N(Rι2)(Rι3), ORn, phenyl or halogen;
R11 is hydrogen, Ci-C∞alkyl, C2-C2oalkenyI, C3-C8cycloalkyl, benzyl; or Rn is C2-C20alkyl interrupted one or more times by O, or d-doalkenyl interrupted one or more times by O; or R11 is phenyl unsubstituted or substituted by C C4aIkyl or by d-C4alkoxy; R12 an d R13 are each independently of the other hydrogen, Cι-C20alkyl, C2-C20alkenyl, C3-C8cycloalkyl or benzyl; or Rι2 and R13 are C^C^alkyl interrupted one or more times by O, or C2-C20alkenyl interrupted one or more times by O; or Rι2 and R« are phenyl unsubstituted or substituted by d-dalkyl or by d-dalkoxy; or R12 and R13, together with the nitrogen atom to which they are bonded, form a 5- or 6-membered ring uninterrupted or interrupted by O or by NRι4;
Rι4 is hydrogen, Cι-d2alkyl; phenyl unsubstituted or substituted by d-dalkyl or by d-dalkoxy, or benzyl unsubstituted or substituted by d-C4alkyl or by Cι-C4alkoxy, or Ru is C2-Cι2alkyl interrupted one or more times by O; L is a radical -Z-[(A1)a-Y]o-[(A2)b-X]d- ;
X, Y and Z are each independently of the others a single bond, -0-, -S-, -N(Rι6)-, -(CO)-, -(CO)O-, -(CO)N(Rι8)-, -O-(CO)-, -N(Rι6)-(CO)- or -N(Rι6)-(CO)0-;
A! and A2 are each independently of the other CrCι2alkylene, C3-C12cycloalkylene, phenylene, phenylene-Cι-C alkylene or Cι-C alkylene-phenylene-Cι-C4alkylene; a, b, c and d are each independently of the others a number 0 to 4; and R1β is hydrogen, C Cι2alkyl or phenyl; RG is a radical -RdC=CR0Rf ;
CR„R„
RGi and RG2 are each independently of the other -RdC=CRθ- or — c— ; and
Rd, Re and Rf are each independently of the others hydrogen, d-dalkyl, phenyl, (CO)0-(d-C alkyl) or Cι-C4alkylphenyl.
4. A process according to either claim 1 or claim 2, wherein a compound of formula (I) is used.
5. A process according to either claim 1 or claim 2, wherein in addition to the compounds of formula (I), (II), (III) and/or (IV) further photoinitiators (p) are used.
6. A process according to claim 5, wherein the further photoinitiators (p) are compounds of formula V, VI, VII, VIII, IX, X or/and XI
Figure imgf000063_0001
(χl). wherein
Figure imgf000063_0002
∞ is hydrogen or C Cι8alkoxy;
R3o is hydrogen, Cι-Cι8alkyl, Cι-Cι8alkoxy, -0CH2CH2-0R47, morpholino, SCH3, or a group Or
Figure imgf000064_0001
a, b and c are an average of 3; n is a value of from 2 to 10;
G3 and G are each independently of the other terminal groups of the polymeric unit, especially hydrogen or CH3;
R31 is hydroxy, Ci-Ciealkoxy, morpholino, dimethylamino or -0(CH2CH20)m-C Ci6alkyl; R32 and R33 are each independently of the other hydrogen, CrC6alkyl, Cι-Cι6a]koxy or -0(CH2CH20)m-Ci-Ci8alkyl; or R32 and R33 are phenyl or benzyl, those radicals being unsubstituted or substituted by Cι-d2alkyl; or R32 and R33, together with the carbon atom to which they are bonded, form a cyclohexyl ring; m is a number from 1 to 20; but R3ι, R32 and R33 are not all simultaneously C Cι8alkoxy or -0(CHzCH20)m-Ci-Ci6alkyl;
0 O CH,
II I J
R47 is hydrogen, - C - CH = CH, - C -C = CH,
R34, 36, R37 and R3β are each independently of the others hydrogen or methyl; R35 and R39 are hydrogen, methyl or phenylthio, wherein the phenyl ring of the phenylthio radical is unsubstituted or substituted in the 4-, 2-, 2,4- or 2,4,6-position(s) by d-C4alkyl; Rio and R41 are each independently of the other CrC20alkyl, cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenylyl, those radicals being unsubstituted or substituted by halogen, C C 2alkyl, CrC12alkoxy, CrCι2alkylthio or by NR52R53, or R40 and R ι are a S- or N- containing 5- or 6-membered heterocyclic ring or -(CO)R42; R42 is cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenylyl, those radicals being unsubstituted or substituted by halogen, d-C4alkyl or/and by d-C4alkoxy, or R42 is a S- or N- containing 5- or 6-membered heterocyclic ring;
R43 and 44 are each independently of the other cyclopentadienyl unsubstituted or mono-, di- or tri-substituted by Cι-Cι8alkyl, Cι-Cι8alkoxy, cyclopentyl, cyclohexyl or by halogen; R45 and R46 are each independently of the other phenyl which is substituted by fluorine atoms or CF3 in at least one of the two positions ortho to the titanium -carbon bond and may contain, as further substituents at the aromatic ring, polyoxaalkyl or pyrrolinyl unsubstituted or substituted by one or two Cι-Cι2alkyl, di(Cι-Ci2alkyl)aminomethyl, morpholinomethyl, C2-C4alkenyl, methoxymethyl, ethoxymethyl, trimethylsilyl, formyl, methoxy or phenyl substituents,
or —
Figure imgf000065_0001
49 and 50 are each independently ry1 ;
R4S, R of the- others hydrogen, halogen, C2-Cι2alkenyl, C Cι2alkoxy, C2-Cι2alkoxy interrupted by from one to four O atoms, cyclohexyloxy, cyclo- pentyloxy, phenoxy, benzyloxy, or phenyl or biphenylyl each unsubstituted or substituted by d-dalkoxy, halogen, phenylthio or by d-dalkylthio, wherein R48 and R50 are not both simultaneously hydrogen and in the radical
at least one radical R48 or R5o is Cι-Cι2alkoxy, C2-Cι2alkoxy interrupted by
Figure imgf000065_0002
from one to four O atoms, cyclohexyloxy, cyclopentyloxy, phenoxy or benzyloxy;
Figure imgf000065_0003
R51 is Cι-C8alkyl, phenyl or cyclohexyl;
R52 and R53 are each independently of the other hydrogen; Cι-Cι2alkyl uninterrupted or interrupted by O atoms and unsubstituted or substituted by OH or by SH; or R52 and R53 are
C2-Cι2alkenyl, cyclopentyl, cyclohexyl, benzyl, phenyl;
RM is hydrogen,
Figure imgf000066_0002
or a group ;
Figure imgf000066_0001
R55, R56, R57, R58 and R59 are each independently of the others hydrogen; Cι-Cι2alkyl which is unsubstituted or substituted by OH, C C4alkoxy, phenyl, naphthyl, halogen or by CN and may be interrupted by one or more O atoms; or ^, Rsa, R57, Rss and R59 are d-C alkoxy, Cι-C alkylthio or NR52R53;
Y-i is a divalent aliphatic or aromatic radical, especially C -Cι2alkylene; x is O or 1;
Reo is phenyl, naphthyl, or, when x is 0, 9H-carbazol-3-yl, or (9-oxo-9H-thioxanthen-2-yl)-, all those radicals being unsubstituted or substituted by one or more SR63, OR&), NR52R 3, halogen, Ci-Caalkyl, phenyl, benzyl, -(CO)-Cι-C4alkyl, -(CO)-phenyl or -(CO)-phenylene- d-C4alkyl substituents;
Rm is C4-C9cycloalkanoyl; Cι-Cι2alkanoyl unsubstituted or substituted by one or more halogen, phenyl or CN substituents; or Rβι is C -Cθalkenoyl, with the proviso that the double bond is not conjugated with the carbonyl group; or Rβι is benzoyl unsubstituted or substituted by one or more d-Cβalkyl, halogen, CN, ORe4, SR63 or NR52R53 substituents; or R61 is C2-C6alkoxycarbonyl, benzyloxycarbonyl; or phenoxycarbonyl unsubstituted or substituted by one or more Cι-C8alkyl or halogen substituents;
RB2 is hydrogen, phenyl or benzoyl, the radicals phenyl and benzoyl being unsubstituted or substituted by d-C6alkyl, phenyl, halogen, ORw, S β3 or by NRs^^; or R62 is C C2oalkyl or C2-Ci2alkoxycarbonyl, the radicals d-doalkyl and C2-Ci2alkoxycarbonyl being unsubstituted or substituted by OH and uninterrupted or interrupted by one or more O atoms; or Rβ2 is C2-C20alkanoyl, benzyl, benzyl-(CO)-, Cι-C6alkyl-S02- or phenyl-S02-; Rβ3 and R∞ are each independently of the other hydrogen or C Cι2alkyl unsubstituted or substituted by OH, SH, CN, phenyl, (CO)0-d-C4alkyl, 0(CO)-Cι-C4alkyl, COOH, O(CO)- phenyl, and such unsubstituted or substituted Ci-Caalkyl may be interrupted by one or more O atoms; or RM and R64 are cyclohexyl, or phenyl unsubstituted or substituted by Cι-Cι2alkyl, C Cι2alkoxy or by halogen, or phenyl-Cι-C3alkyl;
Res, εβ and R67 are each independently of the others hydrogen, d-C4alkyl, CrC haloalkyl, CrC4alkoxy, chlorine or N(Cι-C4alkyl)2; Res is hydrogen, d-dalkyl, Ci-dhaloalkyl, phenyl, N(d-C4alkyl)2, COOCH3,
Figure imgf000067_0001
together are -S-.
7. A process according to any one of preceding claims 1 to 6, wherein the photoinitiators of formula (I), (II), (111) and/or (IV) or mixtures thereof with monomers or oligomers are used in combination with one or more liquids (such as solvents or water) in the form of solutions, suspensions and emulsions.
8. A process according to claim 2, wherein in process step d1) a photopolymerisable composition, comprising at least one ethylenically unsaturated monomer or/and oligomer and at least one photoinitiator and/or coinitiator, is applied to the pretreated substrate and cured by means of UVΛ/IS radiation.
9. A process according to either claim 1 or claim 2, wherein as plasma gas there is used an inert gas or a mixture of an inert gas with a reactive gas.
10. A process according to claim 9, wherein air, H2, COz, He, Ar, Kr, Xe, N2, 02 or H20 are used singly or in the form of a mixture.
11. A process according to either claim 1 or claim 2, wherein the applied photoinitiator layer has a layer thickness of up to 500 nm, preferably from a monomolecular layer up to 200 nm.
12. A process according to either claim 1 or claim 2, wherein process step b) is carried out immediately after process step a) or within 24 hours after process step a).
13. A process according to either claim 1 or claim 2, wherein the concentration of the photoinitiator or photoinitiators in process step b) is from 0.01 to 99.5 %, preferably from 0.1 to 80 %.
14. A process according to either claim 1 or claim 2, wherein process step c) is carried out immediately after process step b) or within 24 hours after process step b).
15. A process according to either claim 1 or claim 2, wherein drying in process step c) is carried out in an oven, with warm gas, heated rollers or an IR or microwave radiator or by absorption.
16. A process according to either claim 1 or claim 2, wherein irradiation in process step c) is carried out using a source that emits electromagnetic waves having wavelengths in the range of from 200 nm to 700 nm or by means of an electron beam.
17. A process according to claim 1 , wherein portions of the photoinitiators, or mixtures thereof with monomers and/or oligomers, applied in process step b) that have not been crosslinked after irradiation in process step c) are removed by treatment with a solvent and/or water and/or mechanically.
18. A process according to claim 2, wherein after irradiation in process step d1 ) portions of the coating are removed by treatment with a solvent and/or water and/or mechanically.
19. A strongly adherent coating obtainable by a process according to any one of preceding claims 1 to 18.
20. Use of a compound of formula (I), (II), (111) or (IV) according to claim 1 in a process according to any one of preceding claims 1 to 19.
21. A compound of formula (P), (II'), (IIP) or (IV)
IN-Q-RG (P)
IN-Q-RG1-Q1-H (IP)
Figure imgf000068_0001
IN-Q-RGι-Qι-RG2-Q2-INι (IV), wherein IN and IN1 are each independently of the others a monoacylphosphine, monoacylphosphine oxide or monoacylphosphine sulfide photoinitiator group; Q, Q1 and Q2 are a single bond or a spacer group of formula -Zr[(Aι)a-Y]c-[(A2)b-X]d-, X and Y are each independently of the other a single bond, -0-, -S-, -N(Rι6)-, -(CO)-, -(CO)O-, -(CO)N(Ri6)-, -O-(CO)-, -N(Rιβ)-(CO)- or -N(Rι6)-(CO)0-; Z, is a single bond, -S-, -(CO)-, -(CO)O-, -(CO)N(Rι6)-, -O-(CO)-, -N(Rι6)-(CO)- or -N(R1β)-(CO)0-;
A, and A2 are each independently of the other Cι-Cι2alkylene, C3-Cι2cycloalkylene, phenylene, phenylene-d-dalkylene or C1-C alkylene-phenylene-Cι-C4alkylene; a, b, c and d are each independently of the other a number 0 to 4; Ri6 is hydrogen, Ci-Caalkyl or phenyl;
RG is a monovalent radical having at least one ethylenically unsaturated C=C bond; and RGi and RG2 are each independently of the other a divalent radical having at least one ethylenically unsaturated C=C bond; with the proviso that compounds of formula (I) wherein the spacer group Q is methylene and at the same time RG is vinyl and compounds of formula (I) wherein the spacer group Q is a single bond and at the same time RG is allyl are excluded; and with the proviso that when Zi is a group -O(CO)-, a and c are not 0 and at the same time Ai is not a single bond.
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