WO2003068785A1 - Mono- and biacylphosphine derivatives - Google Patents

Mono- and biacylphosphine derivatives Download PDF

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Publication number
WO2003068785A1
WO2003068785A1 PCT/EP2003/001070 EP0301070W WO03068785A1 WO 2003068785 A1 WO2003068785 A1 WO 2003068785A1 EP 0301070 W EP0301070 W EP 0301070W WO 03068785 A1 WO03068785 A1 WO 03068785A1
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het
alkyl
acyl
bisacylphosphine
groups
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PCT/EP2003/001070
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German (de)
French (fr)
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Ralf Noe
Erich Beck
Matthias Maase
Andreas Henne
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Basf Aktiengesellschaft
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Priority to AU2003205731A priority Critical patent/AU2003205731A1/en
Publication of WO2003068785A1 publication Critical patent/WO2003068785A1/en

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    • 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 Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/65502—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a three-membered ring
    • 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 Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/32—Esters thereof
    • C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/3247—Esters of acids containing the structure -C(=X)-P(=X)(R)(XH) or NC-P(=X)(R)(XH), (X = O, S, Se)
    • C07F9/3252—Esters of acids containing the structure -C(=X)-P(=X)(R)(XH) or NC-P(=X)(R)(XH), (X = O, S, Se) containing the structure -C(=X)-P(=X)(R)(XR), (X = O, S, Se)
    • 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 Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/36—Amides thereof
    • 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 Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4062—Esters of acids containing the structure -C(=X)-P(=X)(XR)2 or NC-P(=X)(XR)2, (X = O, S, Se)
    • C07F9/4065—Esters of acids containing the structure -C(=X)-P(=X)(XR)2, (X = O, S, Se)
    • 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 Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/44—Amides thereof
    • C07F9/4403—Amides thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/443—Amides of acids containing the structure -C(=Y)-P(=X)(XR)-N or NC-(P(=X)(XR)-N )
    • 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 Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/59—Hydrogenated pyridine rings
    • 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 Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6509—Six-membered rings
    • C07F9/650952—Six-membered rings having the nitrogen atoms in the positions 1 and 4

Definitions

  • the invention relates to special mono- and bisacylphosphine derivatives, processes for their preparation and their use as photoinitiators for the photopolymerization of ethylenically unsaturated compounds.
  • Monoacylphosphine oxides are known as photoinitiators e.g. from EP-A 7508.
  • Bisacylphosphine oxides and their use as photoinitiators are known, for example, from EP-A 184 085.
  • WO 00/17212 describes organophosphorus compounds in which acylphosphine oxides are connected via a spacer group to an N-acryloyl radical.
  • WO 99/52515 describes their use as pharmaceuticals.
  • this spacer group can also contain an ether or a keto group.
  • EP-A 413 657 describes mono- and diacylphosphine oxides, in which a substituted or unsubsti- Acylphosphinoxidiser about tutechnischs phenylene, xylylene, cyclohexyl or Ci-C ⁇ alkylene with a different, for example, acrylic substituted Phosphinoxidein- is connected integral.
  • EP-A 670 323 discloses dimeric bisacylphosphine oxides in which the phosphine oxide structures are connected to one another by spacers. The spacer is always bound to a phosphorus atom with a carbon atom.
  • EP-A 62 839 describes acylphosphine compounds which carry acryloxy substituents in an associated ammonium ion.
  • DE-A 195 24 812 describes radiation-curable (meth) acrylates in which (meth) acrylic groups are linked to aceto or benzophenone units.
  • JP 8-151404 describes (meth) acrylates which are connected via a spacer group to aceto-, benzo- or phosphinoxophenones.
  • EP-A 281 941 describes co-reactive photoinitiators, RG-A-IN, in which a functional reactive group RG, e.g. Vinyl or acrylic, but also OH, NH, NCO etc. via a spacer A with a photoinitiator basic structure IN, e.g. Aceto-, benzo- or acylphosphine oxophenone, and their use in photopolymerization.
  • RG functional reactive group
  • IN e.g. Aceto-, benzo- or acylphosphine oxophenone
  • EP-A 281 941 does not name acylphosphine oxides for which this concept is applicable, nor does it disclose a process for their preparation.
  • WO 00/24527 describes the use of photoinitiators e.g. of the RG-A-IN type, wherein
  • A is a spacer group or single bond
  • RG is at least one functional, ethylenically unsaturated group
  • Radical sites are generated on the substrate, for example by discharge or radiation, the organic photoinitiators with at least one ethylenically unsaturated group are applied to the substrate and are allowed to react there with the radical sites generated, the substrate thus precoated with at least one ethylenically unsaturated monomer or Oligomers are coated and cured by means of UV / VIS radiation and a metal, semimetal or metal oxide is deposited from the gas phase in the presence of UV light.
  • WO 00/24527 gives no technical teaching for the production of such photoinitiators of the phosphine oxide type and gives no indication of the reduction in migration when using such photoinitiators in radiation-curable mixtures.
  • JP-A 08-167172 mentions vinyl pivaloylphenylphosphinate and methyl (meth) acryloylphenylphosphinate as photopolymerization initiators in radiation-curable adhesives.
  • JP-A 08-167172 does not recognize the lower tendency of such phosphine oxides to migrate and gives no indication of their production.
  • the object of the present invention was to develop build-in photoinitiators which have a lower tendency to migrate than the conventional photoinitiators of the phosphine oxide type, but have a similar reactivity.
  • R 1 , R 2 Ci - Ci 8 ⁇ alkyl optionally by one or more
  • Oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted C 2 - cis alkyl, C 2 - Ci ⁇ -alkenyl, C 6 - C ⁇ -aryl, C 5 - C ⁇ 2 cycloalkyl or a five to six-membered heterocycle containing oxygen, nitrogen and / or sulfur atoms, where the radicals mentioned can each be substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, R 2 also optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles Ci - Cis-alkoxy or R 1 - (C Y) -,
  • R 3 is hydrogen, Ci to C 4 alkyl, S0 3 H, phenyl or acetyl,
  • R 4 is hydrogen, C 1 to C -alkyl, COOR 3 or C 6 -C 8 -aryl or arylsulfonyl which is optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles,
  • X is a spacer substituted n times with groups RG,
  • RG is a radical or cationically polymerizable group or a group which can interact with the polymer being formed and
  • n is a natural number from 1 to 10 and
  • X can also be unsubstituted or halogen, Ci-Cs-alkyl, C 2 -Cs-alkenyl, carboxy, carboxy-Ci-Cs-alkyl, -C-C 2 o ⁇ acyl, Ci-Cs-alkoxy, C 6 - -C aryl, hydroxyl, hydroxy-substituted Ci-C ⁇ -alkyl or n-fold substituted by groups RG C 6 -C ⁇ 2 -arylene, C 3 -C ⁇ -cycloalkylene, C ⁇ -C 2f j -alkylene or by one or more Oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups and / or by one or more - (CO) -, -0 (C0) 0-, - (NH) (CO) 0-, -0 ( CO) (NH) -, -0 (C0) - or -
  • Radically polymerizable groups are, for example, isolated ethylenically unsaturated groups, conjugated unsaturated groups, vinyl aromatic groups, vinyl and vinylidene chloride groups, N-vinyl amides, vinyl pyrrolidones, vinyl lactams, vinyl esters, (meth) acrylic esters or acrylonitriles.
  • Cationically polymerizable groups are, for example, isobutylene units or vinyl ethers.
  • C 1 -C 8 alkyl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, Heptyl, octyl, 2-ethylhexyl, 2, 4, 4-trimethyl-5-pentyl, decyl, dodecyl, tetradecyl, hetadecyl, octadecyl, 1,1-dimethylpropyl, 1, 1-dimethylbutyl, 1, 1, 3, 3 -Tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, ⁇ , ⁇ -dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-
  • Ci - Ci 8 alkoxy for example methoxy, ethoxy, n-propyloxy, iso-propyloxy, n-butyloxy, iso-butyloxy, sec. -Butyloxy, tert. -Butyloxy, 6-hydroxy-l, 4-dioxo-hexyl, 9-hydroxy-l, 4, 7-trioxononyl, 12-hydroxy-l, 4, 7, 10-tetraoxo-
  • 35 dodecyl, 6-methoxy-l, 4-dioxohexyl, 9-methoxy-l, 4, 7-trioxononyl, 12-methoxy-l, 4,7, 10-tetraoxododecyl, 6-ethoxy-l, 4-dioxohexyl, 9 -Ethoxy-l, 4, 7-trioxononyl, 12-ethoxy-l, 4,7, 10-tetraoxododecyl, 8-hydroxy-l, 5-dioxooctyl, 12-hydroxy-l, 5, 9-trioxooctyl, 16-hy droxy-1, 5,9, 13-tetraoxohexadecyl, 8-methoxy-l, 5-dioxooctyl,
  • the number of oxygen and / or sulfur atoms and / or imino groups is not restricted. As a rule it is not more than 5 in the rest, preferably not more than 4 and very particularly preferably not more than 3.
  • Substituted and unsubstituted imino groups can be, for example, imino, methyli ino, iso-propylimino, n-butylimino or tert-butylimino.
  • C 2 - cis alkenyl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example vinyl, 1-propenyl, allyl, methallyl, 1, 1-dimethylallyl, 2-butenyl, 2-hexenyl, octenyl, undecenyl , Dodecenyl, octadecenyl, 2-phenylvinyl, 2-methoxyvinyl, 2-ethoxyvinyl, 2-methoxyallyl, 3-methoxyallyl, 2-ethoxyallyl, 3-ethoxyallyl or 1- or 2-chlorovinyl,
  • Ce - -C aryl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example phenyl, tolyl, xylyl, ⁇ -naphthyl, ⁇ -naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, Me- thylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert.
  • C 5 -C 2 -cycloalkyl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, methoxycyclohexyl, diethylcyclohexyl, Dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl,
  • a five- to six-membered heterocycle containing oxygen, nitrogen and / or sulfur atoms for example furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrylidyl, dimethylpyrylidyl Difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert.
  • -Butylthiophenyl
  • Ci to C 4 alkyl for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert. -Butyl and
  • aryl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles C 6 -C 2 aryl or arylsulfonyl, for example phenyl, 2, 6-dinitrophenyl, 2, 4-dinitrophenyl, 2-nitrophenyl, 4-nitrophenyl, Formyl, acetyl, propionyl, carbamoyl, phenylsulfonyl or 4-methylphenylsulfonyl.
  • radicals having one to three carbon atoms it is up to 3 substituents, preferably up to 2 and particularly preferably up to one.
  • radicals with four to six carbon atoms it is generally up to 4 substituents, preferably up to 3 and particularly preferably up to one.
  • radicals with more than seven carbon atoms it is generally up to 6 substituents, preferably up to 4 and particularly preferably up to two.
  • X can be, for example, 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene, 1,6-hexylene, 2-methyl-1,3-propylene, 2-ethyl- l, 3-propylene, 2, 2-dimethyl-l, 3-propylene, 2,2-dimethyl-l, 4-butylene, 1-oxa-l, 3-propylene, 1, 4-dioxa-l, 6-hexylene,
  • X can furthermore represent a spacer group, as is essentially described in WO 00/24527. Accordingly, X can be used for
  • Z 1 , Z 2 , and Z 3 each independently for a single bond, -0-, -S-, -N (R 8 ) -, - (CO) -, - (CO) O-, - ( CO) N (R 8 ) -, -O- (CO) -, -N (R 8 ) - (CO) - or -N (R 8 ) - (CO) 0-,
  • Ci - C alkylene C 3 - C ⁇ 2 cycloalkylene, phenylene, phenylene-Ci - C -alkylene or Ci - C -alkylene-phenylene-Ci - C 4 -alkylene and
  • a, b, c, d independently of one another represent the numbers 0 to 4.
  • R 8 is hydrogen, Ci to Cis-alkyl or phenyl.
  • Ci - C alkylene therein denotes linear or branched alkylene, e.g. Methylene, 1,2-ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 1,1-dimethyl-1,2-ethylene or 1,2 -Dime- 1, 2-ethylene,
  • C 1 -C 2 -cycloalkylene for example cyclopropylene, cyclopentylene,
  • Cyclohexylene, cyclooctylene, cyclododecylene, Phenylene-Ci-C-alkylene stands for phenylene which is substituted in one position of the aromatic ring with Ci-C-alkylene, for example 1 ', 4-tolylene or 1', 1 '-dimethyl-1', 4-Toluy- len,
  • Ci - C -alkylene-phenylene-C ⁇ -C -alkylene stands for phenylene, which is substituted in two positions of the aromatic ring with Ci - C -alkylene, for example 2, 4-dimethylphenyl-l ', 1' '-en or 1 ', 1' -dimethyl-2, 4-dimethylphenyl-l ', 1 "' s.
  • Z 1 , Z 2 , Z 3 , a, b, c and d are as defined above.
  • RG means a residue of the formula
  • R 5 , R 6 , R 7 therein mean C 1 -C 4 -alkyl, optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, C 2 -C 3 -alkyl, Ci-Cia -Alkoxy, C 2 - cis-alkenyl, C 6 - -CC aryl, C 5 - C 2 cycloalkyl or a five- to six-membered heterocycle having oxygen, nitrogen and / or sulfur atoms, the radicals mentioned in each case can be substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles,
  • RG can, for example, vinyl, vinyloxy, 1-propen-1-yl, 1-propen-2-yl, 2-buten-2-yl, 3-methyl-2-buten-2-yl, 2-vinylphen-1 -yl, 3-vinylphen-l-yl, 3-vinylphen-l-yl, 2-phenylethen-l-yl, 2- (4-methoxyphenyl) ethen-1-yl, acrylic, methacrylic, crotonyl, acryloxy , Acrylamido, methacryloxy or crotonyloxy.
  • RG can be a group
  • R 9 each identically or differently hydrogen or -CC-alkyl, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, seJ-butyl or tert. -Butyl, can be.
  • the groups X-RG n can furthermore be, for example,
  • Such XRG n can be, for example, 2-dimethylaminoethoxy, 2-aminoethoxy, l-aza-3-aminoprop-l-yl, 1,4-diaza-6-aminohexyl, 4-aza-l-oxa-6-aminohexyl, 4- Aza-l-oxa-6-hydroxyhexyl, l-aza-3-hydroxy-1- (2 'hydroxyethyl) propyl, piperazin-1-yl, 4-methyl-piperazine-l-yl or 2' -Piperazinoethoxy.
  • X can also be, for example
  • XRG n bears several RG groups, it can be, for example where Z 4 , Z 5 , Z 6 single bond, O, S, NH, NR 10 , CH 2 , CHR 10 , CR 10 2 , - (CO) -, - (CO) O-, - ( CO) N (R 10 ) -, -O- (CO) -, -N (R 10 ) - (CO) - or -N (R 10 ) - (CO) O-,
  • A, A 4 , A 5 single bond Ci - C 4 alkylene, C 3 - C 2 cycloalkylene, phenylene, phenylene-Ci - C 4 alkylene or Ci - C 4 alkylene-phenylene-C - C 4 alkylene .
  • e an integer between 0 and 20 and
  • R 10 each independently of one another hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 alkoxy, hydroxy, hydroxy C 1 -C 4 alkyl, carboxyl, C 1 -C 4 -acyl, carboxy C 1 -C 4 alkyl, C 6 -C ⁇ 2 aryl, -O-RG, -CH 2 OH or -CH 2 0-RG.
  • R 1 is preferably phenyl, tolyl, xylyl, ⁇ -naphthyl, ⁇ -naphthyl, 2- 3- or 4-chlorophenyl, 2,6- or 2, 4-dichlorophenyl, 2,4,6-trichlorophenyl, 2- , 3- or 4-methylphenyl, 2,6- or 2, -dimethylphe- nyl, 2, 4, 6-trimethylphenyl, 2-, 3- or 4-ethylphenyl, 2,6- or 2, 4-diethylphenyl, 2-, 3- or 4-iso-propylphenyl, 2-, 3- or 4 -tert.-butylphenyl, 2-, 3- or 4-methoxyphenyl, 2,6- or 2, 4-dimethoxyphenyl, 2,6- or 2, 4-diethoxyphenyl, methylnaph- 5 thyl, 2, 6-dimethylphenyl, 2 , 4, 6-trimethylphenyl, 2, 6-dimeth
  • R 1 is particularly preferably phenyl, tolyl, ⁇ -naphthyl, ⁇ -naphthyl,
  • R 1 is very particularly preferably phenyl, 2-methylphenyl, 2-methoxyphenyl, 2-chlorophenyl, ⁇ -naphthyl, 2, 6-dichlorophenyl, 2,4, 6-trichlorophenyl, 2, 6-dimethylphenyl, 2 , 4, 6-trimethylphenyl, 2,6-diethylphenyl, 2, 6-dimethoxyphenyl, 2,6-diethoxyphenyl, 2, 6-dimethylphenyl, 2, 4, 6-trimethylphenyl, 2, 6-dimethoxyphenyl, 2nd , 6-dense
  • R 1 is in particular phenyl, 2, 6-dichlorophenyl, 2, 4, 6-trichlorophenyl, 2, 6-dimethylphenyl, 2, 4, 6-trimethylphenyl or 2,6-dimethoxyphenyl.
  • R 2 is preferably 2, 4, 4-trimethylpentyl, benzyl, p-chlorobenzyl,
  • 40 iso-propyloxy, n-butyloxy, iso-butyloxy, sec. -Butyloxy, tert. -Butyloxy, 6-hydroxy-l, 4-dioxohexyl, 9-hydroxy-l, 4, 7-trioxononyl, 12-hydroxy-l, 4,7, 10-tetraoxododecyl, 6-methoxy-l, 4-dioxohexyl, 9 -Methoxy-l, 4, 7-trioxononyl, 12-methoxy-l, 4,7, 10-tetraoxododecyl, 6-ethoxy-l, 4-dioxohexyl, 9-ethoxy-l, 4, 7-trioxononyl,
  • R 2 is particularly preferably benzyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, methoxy, ethoxy, n-propyloxy, iso-propyloxy, n-butyloxy, iso-butyloxy, sec. -Butyloxy, tert.
  • R 2 is very particularly preferably methoxy, ethoxy, n-propoxy, iso-propoxy, n-butyloxy, sec-butyloxy, iso-butyloxy, tert-butyloxy, 6-hydroxy-l, 4-dioxohexyl, 9-hydroxy-l, 4, 7-trioxononyl, 12-hydroxy-1, 4, 7, 10-tetraoxododecyl, 8-hydroxy-l, 5-dioxooctyl, 12-hydroxy-1, 5, 9-trioxooctyl, 16-hydroxy- l, 5,9,13-tetraoxohexadecyl, 10-hydroxy-l, 6-dioxodecyl, 15-hydroxy-l, 6, 11-trioxopentadecyl, phenyl, xylyl, ⁇ -naphthyl, ß-naphthyl, 4-diphenylyl, 2- , 3-
  • R 2 is in particular methoxy, ethoxy, n-propoxy, iso-propoxy, n-butyloxy, sec-butyloxy, iso-butyloxy, tert-butyloxy, phenyl, 4-diphenylyl, 2-, 3- or 4- Chlorophenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-methoxyphenyl or 2-, 3- or 4-ethoxyphenyl.
  • R 2 is specifically phenyl, methoxy or ethoxy.
  • Y is preferably 0, S or NR 3 .
  • Y is particularly preferably 0 or S and very particularly preferably 0.
  • Z is preferably 0, S, NR 3 or a free electron pair, particularly preferably 0, S or a free electron pair, very particularly preferably 0 or S and in particular 0.
  • R 3 is preferably hydrogen, methyl, tert. -Butyl, phenyl or S0 3 H, particularly preferably hydrogen, tert. -Butyl, phenyl or S0 3 H and very particularly preferably hydrogen, tert. -Butyl or phenyl.
  • R 4 is preferably hydrogen, methyl, phenyl, 2, 4-dinitrophenyl, carbamoyl, phenylsulfonyl or 4-methylphenylsulfonyl, particularly preferably hydrogen, phenyl, 2, 4-dinitrophenyl or phenylsulfonyl, very particularly preferably hydrogen, 2, 4-dinitrophenyl or phenylsulfonyl and especially hydrogen or 2,4-dinitrophphenyl.
  • R 5 is preferably hydrogen, methoxy, methyl or ethyl.
  • R 5 is particularly preferably hydrogen or methyl.
  • R 5 is very particularly preferably hydrogen.
  • R 6 is preferably hydrogen, methoxy, phenyl, methyl or ethyl, particularly preferably hydrogen, phenyl or methyl and very particularly preferably hydrogen.
  • R 7 is preferably hydrogen, methoxy, phenyl, methyl or ethyl, particularly preferably hydrogen, phenyl or methyl and very particularly preferably hydrogen.
  • R 8 is preferably hydrogen, methyl, ethyl, n-butyl or phenyl, particularly preferably hydrogen or methyl and very particularly preferably hydrogen.
  • n is preferably from 1 to 10, particularly preferably from 1 to 5, very particularly preferably from 1 to 3 and in particular 1.
  • R 2 is 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl, methoxy, n-propoxy, iso-propoxy, n-butoxy, seic-butoxy, iso -Butoxy or tert-butoxy.
  • R 1 are ortho-substituted, for example 2-methylphenyl, 2-methoxyphenyl or 2-chlorophenyl.
  • the present invention furthermore relates to a process for the preparation of acyl and bis-acylphosphine derivatives of the formula (I), in which a substance HX-RG n or ⁇ X-RG n with a compound of the formula (III),
  • FG a leaving group of the structure -F, -Cl, -I, -CN, -OCN, -SCN, -N + R 15 R 16 R 17 , -0 (C0) R 14 , -0 (CO) OR 14 , - 0 (C0) NR 14 , -N (C0) NR 14 , -0 (S0) C1, -0 (S0 2 ) C1, -0 (S0 2 ) R 14 , -0 (S0 2 ) OR 14 , -0 (C0) C1, -0 (NO) OR 14 , -SR 14 , -Br, - (NR 12 ) -NR 13 R 18 or
  • R 12 is hydrogen, Ci to C 4 alkyl, S0 3 H, phenyl or acetyl,
  • R 13 is hydrogen, Ci to C 4 alkyl, COOR 3 or C ⁇ -Cj-aryl or arylsulfonyl which is optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles,
  • R 14 optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles Ci - Ci ⁇ alkyl, optionally interrupted by one or more oxygen, nitrogen and / or sulfur atoms C 2 - cis alkyl, optionally by aryl, Alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles substituted Ci - Cis-alkoxy, optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles C - Ci ⁇ -alkenyl, optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles C ⁇ , - C ⁇ 2 -aryl, optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles substituted C 5 - C ⁇ 2 cycloalkyl
  • R 17 optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles Ci - Cis-alkyl or optionally interrupted by one or more oxygen, nitrogen and / or sulfur atoms C 2 - Ci ⁇ -alkyl and
  • Rl8 is hydrogen or Ci to C alkyl
  • the present invention furthermore relates to dimeric acyl and bisacylphosphine oxides of the formula (II),
  • R 1 , R 2 , Y and Z have the meanings given above and R 1 ', R 2 ', Y 'and Z' have the same meanings as R 1 , R 2 , Y and Z, but can be different from these ,
  • X has the above meaning and Het 1 and Het 2 independently of one another mean 0, S or NR 9 .
  • the phosphine derivatives of the formula (III) can be prepared by a process in which a substance of the formula
  • R 1 , R 2 , Y and Z have the meaning given above and
  • X ' is hydrogen or a cation
  • Cations can be, for example, those as listed in EP-A 62 839, that is, equivalents of a cation of the 1st to 3rd main group of the periodic table with a molecular weight below 138 or ammonium ions derived from quaternary ammonium ions or triethylene diammonium ions.
  • Agents which convert the group -OX 'into the group -FG are known per se to the person skilled in the art. Examples include phosgene (C0C1 2 ), thionyl chloride (S0C1 2 ), sulfuryl chloride (S0 2 C1 2 ), phosphorus trichloride (PCl 3 ), phosphorus oxychloride (P0C1 3 ), phosphorus pentachloride (PC1 5 ), oxalyl chloride ((C0C1) 2 ), hydrogen chloride (HC1), chlorine gas (Cl 2 ), N-chlorine compounds such as N-chlorosuccinimide, alkali fluoride, cobalt (III) fluoride, halogen fluoride, antimony fluoride, molybdenum fluoride, hydrogen fluoride, hydrogen fluoride / pyridine mixtures, xenon fluoride and other noble gas compounds, gaseous fluorine, sulfur tetrafluoride
  • Examples of compounds of the formula H-Het x -X-Het 2 -H, or their anions, are polyethylene glycols with a molecular weight between 106 and 898, especially ethylene glycol, diethylene glycol, Triethylene glycol, tetraethylene glycol, 1, 2-propylene glycol, poly-1, 2-propylene glycol with a molecular weight between 134 and 1178, 1, 3-propylene glycol, poly-1, 3-propylene glycol with a molecular weight between 134 and 1178, 1, 4- Butanediol, poly-THF with a molecular weight between 162 and 1458, 1, 6-hexanediol, 1, 8-0ctanediol, 1,10-decanediol, 1, 12-dodecanediol, 2-ethylhexan-l, 3-diol, 2 , 4-Diethyloc- tan-1, 3-diol, trimethylolpropane,
  • Polether and polyesterols with an average OH functionality of 2 to 10, which preferably have a molecular weight of 200 to 2000, are also conceivable.
  • R 2 is 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl, methoxy, n-propoxy, iso-propoxy, n-butoxy, seJc-butoxy, iso -Butoxy or tert-butoxy.
  • R 1 are ortho-substituted, for example 2-methylphenyl, 2, 6-dimethyl-1-phenyl, 2-methoxyphenyl, 2,6-dimethyl-1 -phenyl, 2, 6-dichloro-l-phenyl or 2-chlorophenyl.
  • R 1 ', R 2 ', X, Y ', Z', Het 1 and Het 2 are as defined above,
  • R 2 is 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl, methoxy, n-propoxy, iso-propoxy, n-butoxy, seic-butoxy, iso -Butoxy or tert-butoxy.
  • R 1 are ortho-substituted, for example 2-methylphenyl, 2, 6-dimethyl-1-phenyl, 2-methoxyphenyl, 2,6-dimethoxy-1, are also preferred -phenyl, 2, 6-dichloro-l-phenyl or 2-chlorophenyl.
  • reaction of (III) with H-Het 1 -X-Het 2 -H or the corresponding anions or the reaction of (III) with (IV) is carried out, for example, as follows:
  • the reaction with (III) is usually carried out in the presence of 0.9 to 1.5 molar equivalents of an acid scavenger, such as pyridine or a tertiary amine, e.g. Triethylamine, tributylamine, benzyldimethylaamine, dimethyla inopyridine etc., at temperatures between 0 ° C and 100 ° C, preferably between 10 ° C and 80 ° C, the substrate to be reacted, optionally dissolved in a suitable solvent, e.g.
  • an acid scavenger such as pyridine or a tertiary amine, e.g. Triethylamine, tributylamine, benzyldimethylaamine, dimethyla inopyridine etc.
  • (III) can also be used dissolved in a suitable solvent, e.g. the solvents mentioned. If necessary, stirring can be continued, for example 30 to 600 minutes, preferably 60 to 300 minutes, it being possible for the reaction temperature to be raised gradually.
  • the resulting reaction product can be further processed in raw or processed form. If further use in pure form is desired, the product can be purified, for example, by crystallization and solid / liquid separation or by distillation or rectification under reduced pressure.
  • the yields are usually over 75%, mostly over 80% and often over 90%.
  • the mono- and diacyl or dimeric phosphine derivatives described can be used as photoinitiators in photopolymerizable compositions, e.g. Coating agents, lacquers, printing inks, recording materials, aqueous solutions, dispersions and emulsions.
  • radicals R 'and R'' cannot tolerate functionalities which react with an acid chloride R 1 (C0) C1, such as, for example, hydroxyl or amino functions.
  • the functionalized phosphine derivatives according to the invention can be synthesized by reacting a reactive derivative of the formula (III) as described above.
  • R stands for any of the substitutions listed above and the numbers n for any of the numbers described above.
  • the gentle reaction makes it possible to obtain compounds with heteroatom substitution which are more soluble or compatible in various lacquer mixtures, are less migrable with several potential radical centers owing to the polarity of the chain or a higher molecular weight, or can also be incorporated in the polymer due to a copolymerizable structural unit.
  • acylphosphinic acid This can be converted to the derived hydroxyalkyl derivatives using various epoxides.
  • Both acylphosphinic acid, its anions and its hydroxyalkyl derivatives can be reacted with reactive substrates [e.g. B. isocyanates (monoisocyanates, diisocyanates, such as methane diphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), both as 2,4- and 2,6-isomer, and mixtures thereof, isophorone diisocyanate (IPDI), both Mono- and diaducts, and polyisocyanates), acid chlorides, alkylene oxides, epichlorohydrin, etc.] can be functionalized.
  • isocyanates monoisocyanates, diisocyanates, such as methane diphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), both as 2,4- and 2,6-isomer, and mixtures thereof, is
  • the isocyanate grouping still present in monoadducts can be used for further functionalization. Hydrolysis to photoinitiators with a primary amine functionality and thus Michael addition to the acrylate functionality of a radiation-curable resin (see e.g. EP-A 950 219) is possible. Acrylate-functionalized acylphosphine oxide photoinitiators are also available via this synthetic route.
  • the invention furthermore relates to compounds which can be obtained by reacting (I) or (IV), preferably by reacting (IV), with compounds containing reactive groups.
  • Reactive groups are those which are able to form a chemical bond with the group RG or -Het 2 "H of the compounds (I) or (IV).
  • These can be, for example, isocyanate, epoxy, anhydride, acid chloride, ester, acid, carbonate, aldehyde, ⁇ , ⁇ -unsaturated carbonyl, chloroalkyl, bromoalkyl, iodoalkyl or nitrile groups.
  • acid here means, for example, carboxylic acids or sulfonic acids, preferably carboxylic acids.
  • Compounds containing such reactive groups can be, for example, 1,6-hexamethylene diisocyanate (HDI), 2,4- and 2,6-toluenediisocyanate (TDI), 4,4'-methylenedi (phenyl isocyanate) (MDI), isophorone diisocyanate (IPDI) , Bisphenol A mono- and diglycidyl ether, bisphenol B mono- and diglycidyl ether, bisphenol F mono- and diglycidyl ether, 2,2-bis (4-hydroxycyclohexyl) propane mono- and diglycidyl ether, maleic anhydride, phthalic anhydride, ⁇ -caprol ⁇ -caprolactam, vinyloxirane, epichlorohydrin and Adipic acid, (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid and the esters of these acids.
  • HDI 1,6-hexamethylene diisocyanate
  • TDI 2,4- and 2,6-to
  • R 11 for example 1,6-hexylene, 3, 5, 5-trimethyl-l, 3-cyclohexylene, 1-methyl-2, 4-phenyl, 1-methyl-2, 6-phenyl, 4, 4 '-diphenylmethy- len, 2, 4 '-diphenylmethylene or 2', 4-diphenylmethylene and
  • R 11 is hydrogen or methyl
  • R 2 ′ 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl, methoxy, n-propoxy, isopropoxy, n-butoxy, seTc-butoxy, are so-butoxy or tert-butoxy.
  • R 1 is ortho-substituted, for example 2-methylphenyl, 2,6-dimethyl-1-phenyl, 2-methoxyphenyl, 2,6-dimethyl- 1-phenyl, 2, 6-dichloro-l-phenyl or 2-chlorophenyl.
  • the low migration of the compounds according to the invention is based on interactions of polar groups in the compounds with the radiation-curable or radiation-hardened mass. As a result of these interactions, the compounds according to the invention are more strongly bound in the polymer than is the case with the commercially available photoinitiators mentioned at the outset.
  • Polar groups that can interact are those that e.g. electrostatic interactions, dipole-dipole interactions, induction (Debye) interactions or hydrogen bonds.
  • hydroxyl, mono-, di- and unsubstituted amino, carboxylic acid, sulfonic acid, ammonium, carboxylate, sulfonate or amide groups preferably hydroxy, mono-, di- and unsubstituted amino, carboxylic acid -, Ammonium, carboxylate or sulfonate groups.
  • Reactive centers are those which are able to form a chemical bond in the radiation-curable composition with groups such as hydroxy, mono- and unsubstituted amino, carboxylic acid, sulfonic acid, carboxylate, sulfonate or amide groups.
  • reactive centers can be, for example, isocyanate, epoxy, anhydride, acid chloride, ester, acid, carbonate, aldehyde, ⁇ , ⁇ -unsaturated carbonyl, chloroalkyl, bromoalkyl, iodoalkyl or Be nitrile groups.
  • Isocyanate, epoxy, ester, acid, carbonate, aldehyde and ⁇ , ⁇ -unsaturated carbonyl groups are preferred.
  • Isocyanate, epoxy, ester and ⁇ , ⁇ -unsaturated carbonyl groups are particularly preferred.
  • Isocyanate, epoxy and ⁇ , ⁇ -unsaturated carbonyl groups are very particularly preferred.
  • the acyl and bisacylphosphine derivatives of the formula (IV) according to the invention can also be incorporated if the corresponding complementary groups which can react with the group -Het 2 -H, for example isocyanate, are present in the radiation-curable composition.
  • cc ⁇ -unsaturated carbonyl compounds, epoxies and the like.
  • the compounds of the formula (Va to c) according to the invention can be processed in radiation-curable compositions if the isocyanate or epoxy functions react with polar groups in the composition.
  • Both mechanisms cause the compounds according to the invention to be anchored in the radiation-curable composition and consequently to reduce migration.
  • acyl and bisacylphosphine derivatives of the formula (III) can also be reacted with compounds which contain a different photoinitiator basic structure and reactive groups, for example benzophenones, acetophenones, hydroxyacetophenones, phenylglyoxylic acids, phenylglyoxylic acid esters, anthraquinones or benzoins.
  • compounds which contain a different photoinitiator basic structure and reactive groups for example benzophenones, acetophenones, hydroxyacetophenones, phenylglyoxylic acids, phenylglyoxylic acid esters, anthraquinones or benzoins.
  • the photoinitiators according to the invention can of course also be used in a mixture with other photoinitiators.
  • These can be, for example, photoinitiators known to those skilled in the art, e.g. those in "Advances in Polymer Science", Volume 14, Springer Berlin 1974 or in K.K. Dietliker, Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints, Volume 3; Photoinitiators for Free Radical and Cationic Polymerization, P.K.T. Oldring (Eds), SITA Technology Ltd, London
  • mono- or bisacylphosphine oxides such as are described in EP-A 7 508, EP-A 57 474, DE-A 196 18 720, EP-A 495 751 or EP-A 615 980, for example 2.4 , 6-trimethylbenzoyldiphenylphosphine oxide (Lucirin ® TPO, BASF AG), ethyl 2, 4, 6-trimethylbenzoylphenylphosphinate (Lucirin ® TPO L, BASF AG), bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (Irga cure® 819 from Ciba Specialty Chemicals), benzophenones, hydroxyacetophenones, phenylglyoxylic acid and their derivatives or mixtures of these photoinitiators.
  • 6-trimethylbenzoyldiphenylphosphine oxide (Lucirin ® TPO, BASF AG)
  • Examples include benzophenone, acetophenone, acetonaphthoquinone, methyl ethyl ketone, Va lerophenone, hexanophenone, ⁇ -phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberon, 4-morpholinobenzophenone, 4-morpholino-deoxybenzoin, p-diacetylbenzene, 4-aminobenzophenone, 4'-methoxy-anthracon, methyl-anthronone, antithephthenone, antithephthenone, antithephthenone, antithephtheno, anthracetaminophenone, - Quinone carbonate, benzaldehyde, ⁇ -tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene, 10-thioxanthenone, 3-acetylphenanthene, 3-acetylindo
  • Non-yellowing or little yellowing photoinitiators of the phenylglyoxalic acid ester type are also suitable, as described in DE-A 198 26 712, DE-A 199 13 353 or WO 98/33761.
  • the compounds of the formulas (I) or (IV) according to the invention react or interact after mixing with the mass to be hardened with their reactive centers or polar groups and are thus bound in a migration-resistant manner.
  • the coating compositions produced with the installable photoinitiators according to the invention are particularly suitable for use in packaging systems, particularly preferably in the food sector.
  • Suitable radiation-curable compositions are, for example, those having from 0.01 to 1.4 mol of reactive centers per 100 g of substance, preferably 0.05 to 1.25, particularly preferably 0.1 to 1, very particularly preferably 0.2 to 0, 75 mol reactive centers and / or from 0.01 to 1.25 mol polar groups, preferably 0.05 to 1.15, particularly preferably 0.1 to 1, very particularly preferably 0.2 to 0.75 mol polar groups Have groups.
  • Radiation-curable compositions which contain from 0.01 to 1.25 mol, preferably 0.05 to 1.15, particularly preferably 0.1 to 1, very particularly preferably 0.2 to 0.75 mol of hydroxyl groups per 100 g of substance and / or from 0.01 to 0.75, preferably 0.05 to 0.66, particularly preferably 0.1 to 0.5 mol of isocyanate groups per 100 g of substance and / or from 0.01 to 1.4 mol, preferably 0.05 to 1.25, particularly preferably 0.1 to 1, very particularly preferably 0.2 to 0.75 mol of epoxy groups per 100 g of substance and / or from 0.01 to 1.4 mol, preferably 0.05 to 1.25, particularly preferably 0.1 to 1, very particularly preferably 0.2 to 0.75 mol of ⁇ , ⁇ -unsaturated carbonyl groups per 100 g of substance.
  • acyl and bisacylphosphine derivatives of the formulas (I) or (IV) according to the invention are generally bound to the reactive centers or polar groups at a temperature between room temperature and the curing temperature of the radiation-curable composition. Typical temperatures are 40-120 ° C, preferably 50-110 ° C and particularly preferably 60-100 ° C.
  • the temperature can remain the same or be raised during the course of the hardening or bonding process.
  • the duration of the thermal treatment is generally between a few minutes and several hours, for example from 1 minute to 5 hours, preferably 2 minutes to 3 hours, particularly preferably 5 minutes to 2 hours and in particular from 10 minutes to 1 hour.
  • the invention accordingly also relates to radiation-curable compositions which comprise radiation-curable compositions which contain at least one reactive center and / or at least one polar group by reacting at least one acyl and bisacylphosphine derivative of the formula (I) or (IV) or prepared by a process according to the invention Composition are available.
  • Another object of the present invention are radiation-curable compositions containing a photoinitiator according to the invention.
  • Radiation curable compositions typically contain
  • compositions are, for example
  • (B) 0-60% by weight, preferably 5-50, particularly preferably 6-40 and in particular 10-30% by weight,
  • the proportion of paint additives (D) can be up to 90% by weight, in this case the proportion of the other components is reduced accordingly.
  • compounds (A) there are radiation-curable, free-radically polymerizable compounds with several, i.e. at least two, copolymerizable, ethylenically unsaturated groups.
  • Compounds (A) are preferably vinyl ether or (meth) acrylate compounds, particularly preferred are the acrylate compounds, i.e. the derivatives of acrylic acid.
  • Preferred vinyl ether and (meth) acrylate compounds (A) contain 2 to 20, preferably 2 to 10 and very particularly preferably 2 to 6 copolymerizable, ethylenically unsaturated double bonds.
  • Such compounds (A) with a content of ethylenically unsaturated double bonds of 0.1-0.7 mol / 100 g are particularly preferred, very particularly preferably 0.2-0.6 mol / 100 g.
  • Suitable reactive diluents are free-radically polymerizable compounds, preferably radiation-curable compounds, with an ethylenically unsaturated, copolymerizable group, or mixtures thereof.
  • Examples include ⁇ , ⁇ -unsaturated carboxylic acids, C 1 -C 20 alkyl (meth) acrylates, vinyl aromatics with up to 20 C atoms, vinyl esters of carboxylic acids containing up to 20 C atoms, ethylenically unsaturated nitriles, vinyl ethers of alcohols containing 1 to 10 carbon atoms and aliphatic hydrocarbons with 2 to 8 carbon atoms and 1 or 2 double bonds.
  • (meth) acrylic acid is used in the context of this document for acrylic acid and methacrylic acid.
  • ⁇ , ⁇ -unsaturated carboxylic acids which can be used are acrylic acid, methacrylic acid, maleic acid or its half-ester, 3-acrylicoxypropionic acid, maleic anhydride, fumaric acid or its half-ester or crotonic acid.
  • Preferred (meth) acrylic acid alkyl esters are those having a C 1 -C 8 -alkyl radical, such as methyl methacrylate, methyl acrylate and ethyl acrylate.
  • Vinyl esters of carboxylic acids with 1 to 20 C atoms are e.g. Vinyl laurate, vinyl stearate, vinyl propionate and vinyl acetate.
  • vinyl aromatic compounds e.g. Vinyltoluene, ⁇ -butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene are suitable.
  • nitriles are acrylonitrile and methacrylonitrile.
  • Suitable vinyl ethers are e.g. Vinyl methyl ether, vinyl isobutyl ether, vinyl hexyl ether and vinyl octyl ether.
  • butadiene, isoprene, as well as ethylene, propylene and isobutylene may be mentioned as non-aromatic hydrocarbons having 2 to 8 carbon atoms and one or two olefinic double bonds.
  • N-vinylformamide, N-vinylpyrrolidone and N-vinylcaprolactam can also be used.
  • Antioxidants, oxidation inhibitors, stabilizers, activators (accelerators), fillers, pigments, dyes, degassing agents, gloss agents, antistatic agents, flame retardants, thickeners, thixotropic agents, flow control agents, binders, antifoams, for example, can be used as typical paint additives (D) , Fragrances, surface-active agents, viscosity modifiers, plasticizers, plasticizers, tackifying resins (tackifiers), chelating agents or compatibilizers.
  • the substrates with the radiation-curable compositions are coated in accordance with customary methods known to the person skilled in the art
  • At least one radiation-curable composition according to the invention for example in the form of a dispersion or without solvent, is applied to the substrate to be coated in the desired thickness and the volatile constituents of the dispersion are removed, if appropriate with heating. If desired, this process can be repeated one or more times.
  • the application to the substrate can in a known manner, for. B. by spraying, spraying, dipping, filling, knife coating, airblade, brushing, rolling, rolling or pouring.
  • the coating thickness is generally in a range from about 3 to 1000 g / m 2 and preferably 10 to 200 g / m 2 .
  • a method for coating substrates in which a coating composition containing a substance according to the invention, optionally in the form of a paint formulation with other paint-typical additives and / or thermally curable resins, is applied to the substrate, optionally dried, thermally at the curing temperature specified above treated and then, optionally at temperatures up to the curing temperature, with active radiation in an oxygen-containing atmosphere, such as Air, or preferably cures under inert gas.
  • a coating composition containing a substance according to the invention optionally in the form of a paint formulation with other paint-typical additives and / or thermally curable resins
  • the process for coating substrates can also be carried out in such a way that, after the mixture or coating formulation according to the invention has been applied, it is first cured with active energy radiation in an oxygen-containing atmosphere, such as air, or preferably under an inert gas, and then thermally treated at the curing temperature. Thermal and radiation curing can of course also take place in parallel.
  • an oxygen-containing atmosphere such as air, or preferably under an inert gas
  • the films formed on the substrate can only be cured thermally. In general, however, the coatings are cured both by irradiation with high-energy radiation and thermally.
  • active energy rays examples include ultraviolet, X-ray and electron beams, ultraviolet and electron beams are preferred.
  • coating of substrates can also be carried out as follows, where:
  • step iii) optionally irradiating the film formed in step ii) with high-energy radiation, the film being prehardened, and then, if appropriate, mechanically processing the object coated with the prehardened film or bringing the surface of the precured film into contact with another substrate,
  • Steps iv) and iii) can also be carried out in the reverse order.
  • H. the film can first be cured thermally and then with high-energy radiation.
  • Typical curing temperatures are 40-120 ° C, preferably 50-110 ° C and particularly preferably 60-100 ° C.
  • the temperature can remain the same or be raised during the course of the hardening process.
  • the curing time is generally between a few minutes and several hours, for example from 1 minute to 5 hours, preferably 2 minutes to 3 hours, particularly preferably 5 minutes to 2 hours and in particular from 10 minutes to 1 hour.
  • Suitable radiation sources for radiation curing are, for example, low-pressure mercury lamps, medium-pressure lamps with high-pressure lamps and fluorescent tubes, pulsed lamps, metal halide lamps, xenon lamps, electrodeless discharge lamps, carbon arc lamps, electron flash devices, which enables radiation curing without a photoinitiator or radiation initiator.
  • High-pressure mercury vapor lamps, lasers, pulsed lamps (flashing light), halogen lamps or excimer lamps are used as radiation sources, for example.
  • the radiation dose usually sufficient for crosslinking in UV curing is in the range from 80 to 3000 mJ / cm 2 .
  • radiation sources can also be used for curing, e.g. two to four.
  • the photoinitiators according to the invention can also be used with a radiation source with little or no UV content. Daylight curing is also possible, although generally slower than curing with active energy rays.
  • the radiation can optionally also in the absence of oxygen, for. B. are carried out under an inert gas atmosphere. Suitable inert gases are preferably nitrogen, noble gases, carbon dioxide or combustion gases. Irradiation can also be carried out by covering the coating material with transparent media.
  • Transparent media are e.g. B. plastic films, glass or liquids, eg. B. water. Particularly preferred is radiation in the manner described in DE-A 199 57 900.
  • a general advantage of the compounds according to the invention is that the solubility of the photoinitiators can be optimally and easily matched to the radiation-curable composition used by structural modifications.
  • Another advantage when using e.g. pigmented radiation-curable compositions is that the absorption of the photoinitiator can be matched to the radiation-curable composition used if the absorption of conventional acylphosphine oxides is hidden, for example, by the pigments.
  • compounds according to the invention it is possible to improve the interactions with the radiation-curable coating systems and thus to optimize the solubility, miscibility, homogenization, etc.
  • compounds 1-2 or 1-21 in the examples make it possible to improve the solubility of the photoinitiators in polyetherol acrylates, which was not possible with conventional acylphosphine oxides.
  • the compounds 1-23 and 1-31, for example, incorporate HALS amine structures.
  • HPLC analysis Kontron Instruments HPLC-Pump 422, Lichrosorb 18 7, Bischoff Chromatography, Shimadzu C-R6A Chromatopac, Mition Roy Spectro Monitor 3100 (230 nm), acetonitrile / water / phosphoric acid (ratio 570: 430: 1) 1.1 ml / min.
  • the lacquer film was applied to a film with a defined layer thickness (15 or 100 ⁇ m).
  • the film was passed through the irradiation apparatus several times at a defined belt speed.
  • the compounds according to the invention have activity similar to that of Lucirin TPO, in some cases in deep curing. are even better (column 3).

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Abstract

The invention relates to mono- and bisacylphosphine derivatives according to formula (I), wherein X represents a spacer and RG represents a radically or cationically polymerizable group or a group that can interact with the forming polymer. The invention also relates to a method for producing these derivatives and to their use as photoinitiators.

Description

Mono- und BisacylphosphinderivateMono- and bisacylphosphine derivatives
Beschreibungdescription
Die Erfindung betrifft spezielle Mono- und Bisacylphosphinderivate, Verfahren zu deren Herstellung sowie deren Verwendung als Photoinitiatoren für die Photopolymerisation von ethylenisch ungesättigten Verbindungen.The invention relates to special mono- and bisacylphosphine derivatives, processes for their preparation and their use as photoinitiators for the photopolymerization of ethylenically unsaturated compounds.
Monoacylphosphinoxide sind als Photoinitiatoren bekannt z.B. aus der EP-A 7508. Bisacylphosphinoxide und ihre Verwendung als Photoinitiatoren sind beispielsweise bekannt aus der EP-A 184 085.Monoacylphosphine oxides are known as photoinitiators e.g. from EP-A 7508. Bisacylphosphine oxides and their use as photoinitiators are known, for example, from EP-A 184 085.
WO 00/17212 beschreibt phosphororganische Verbindungen, in denen Acylphospinoxide über eine Spacergruppe mit einem N-Acryloylrest verbunden sind.WO 00/17212 describes organophosphorus compounds in which acylphosphine oxides are connected via a spacer group to an N-acryloyl radical.
WO 99/52515 beschreibt deren Verwendung als Arzneimittel.WO 99/52515 describes their use as pharmaceuticals.
Nach der WO 00/04031 kann diese Spacergruppe auch eine Ether- oder eine Ketogruppe beinhalten.According to WO 00/04031, this spacer group can also contain an ether or a keto group.
EP-A 413 657 beschreibt Mono- und Diacylphosphinoxide, in denen eine Acylphosphinoxideinheit über substituiertes oder unsubsti- tuiertes Phenylen, Xylylen, Cyclohexyl oder Ci-Cδ-Alkylen mit einer anderen, beispielsweise acrylsubstituierten Phosphinoxidein- heit verbunden ist.EP-A 413 657 describes mono- and diacylphosphine oxides, in which a substituted or unsubsti- Acylphosphinoxideinheit about tuiertes phenylene, xylylene, cyclohexyl or Ci-C δ alkylene with a different, for example, acrylic substituted Phosphinoxidein- is connected integral.
Aus EP-A 670 323 sind dimere Bisacylphosphinoxide bekannt, in denen die Phosphinoxidstrukturen durch Spacer miteinander verbunden sind. Der Spacer ist dabei immer mit einem Kohlenstoffatom an ein Phosphoratom gebunden. EP-A 62 839 beschreibt Acylphosphinverbindungen, die Acryloxysub- stituenten in einem assoziierten Ammoniumion tragen.EP-A 670 323 discloses dimeric bisacylphosphine oxides in which the phosphine oxide structures are connected to one another by spacers. The spacer is always bound to a phosphorus atom with a carbon atom. EP-A 62 839 describes acylphosphine compounds which carry acryloxy substituents in an associated ammonium ion.
DE-A 195 24 812 beschreibt strahlungshärtbare (Meth) acrylate, in denen (Meth) acrylgruppen mit Aceto- oder Benzophenoneinheiten verbunden sind.DE-A 195 24 812 describes radiation-curable (meth) acrylates in which (meth) acrylic groups are linked to aceto or benzophenone units.
JP 8-151404 beschreibt (Meth) acrylate, die über eine Spacergruppe mit Aceto-, Benzo- oder Phosphinoxophenonen verbunden sind.JP 8-151404 describes (meth) acrylates which are connected via a spacer group to aceto-, benzo- or phosphinoxophenones.
Aus der EP-A 281 941 ist die Problematik bekannt, daß Reste oder Abbauprodukte von Photoinitiatoren aus der gehärteten Beschichtung heraus in das umgebende Medium diffundieren (Migration) und dort Probleme bereiten können, beispielsweise wenn es sich um Verpackungsmaterialien für Lebensmittel handelt.From EP-A 281 941 the problem is known that residues or degradation products of photoinitiators diffuse out of the hardened coating into the surrounding medium (migration) and problems there, for example when it comes to packaging materials for food.
EP-A 281 941 beschreibt coreaktive Photoinitiatoren, RG-A-IN, in denen eine funktionelle reaktive Gruppe RG, wie z.B. Vinyl oder Acryl, aber auch OH, NH , NCO etc. über einen Spacer A mit einer Photoinitiatorgrundstruktur IN, wie z.B. Aceto-, Benzo- oder Acylphosphinoxophenon, verbunden ist und deren Verwendung in der Photopolymerisation.EP-A 281 941 describes co-reactive photoinitiators, RG-A-IN, in which a functional reactive group RG, e.g. Vinyl or acrylic, but also OH, NH, NCO etc. via a spacer A with a photoinitiator basic structure IN, e.g. Aceto-, benzo- or acylphosphine oxophenone, and their use in photopolymerization.
EP-A 281 941 nennt jedoch weder Acylphosphinoxide, für die dieses Konzept anwendbar ist, noch offenbart sie ein Verfahren zu deren Herstellung.However, EP-A 281 941 does not name acylphosphine oxides for which this concept is applicable, nor does it disclose a process for their preparation.
Seitdem sind keine einbaubaren Acylphosphinoxide bekannt geworden, die eine vergleichbare Wirksamkeit wie die handelsüblichen Phosphinoxide, wie z.B. 2 , 4, 6-Trimethylbenzoyl diphenylphosphino- xid (Lucirin® TPO, BASF AG), 2 , 4, 6-Trimethylbenzoyl ethoxy phe- nylphosphinoxid (Lucirin® TPO L, BASF AG) oder Bis- (2 , 4, 6-trime- thylbenzoyl) -phenylphosphinoxid (Irgacure® 819 der Firma Ciba Spezialitätenchemie) , aufweisen.Since then, no built-in acylphosphine oxides have become known that have a comparable effectiveness as the commercially available phosphine oxides, e.g. 2, 4, 6-trimethylbenzoyl diphenylphosphino oxide (Lucirin® TPO, BASF AG), 2, 4, 6-trimethylbenzoyl ethoxy phenylphosphine oxide (Lucirin® TPO L, BASF AG) or bis- (2, 4, 6-trime - Thylbenzoyl) phenylphosphine oxide (Irgacure® 819 from Ciba Specialty Chemicals).
WO 00/24527 beschreibt die Verwendung von Photoinitiatoren z.B. vom Typ RG-A-IN, worinWO 00/24527 describes the use of photoinitiators e.g. of the RG-A-IN type, wherein
IN eine Photoinitiatorgrundstruktur,IN a basic photoinitiator structure,
A eine Spacergruppe oder Eiήfachbindung undA is a spacer group or single bond and
RG mindestens eine funktionelle, ethylenisch ungesättigte Gruppe ist,RG is at least one functional, ethylenically unsaturated group,
in einem Verfahren zur Herstellung haftfester Beschichtungen auf einem organischen oder anorganischen Substrat, in demin a process for producing adhesive coatings on an organic or inorganic substrate, in which
auf dem Substrat z.B. durch Entladung oder Bestrahlung Radi- kaistellen erzeugt werden, die organischen Photoinitiatoren mit mindestens einer ethylenisch ungesättigten Gruppe auf das Substrat aufgebracht werden und dort mit den erzeugten Radikalstellen reagieren gelassen werden, - das so vorbeschichtete Substrat mit mindestens einem ethylenisch ungesättigten Monomeren oder Oligomeren beschichtet und mittels UV/VIS-Srahlung gehärtet wird und ein Metall, Halbmetall- oder Metalloxid aus der Gasphase in Gegenwart von UV-Licht abgeschieden wird. WO 00/24527 gibt jedoch keine technische Lehre zur Herstellung solcher Photoinitiatoren vom Phosphinoxid-Typ an und gibt keinen Hinweis auf die Verringerung der Migration bei Verwendung solcher Photoinitiatoren in strahlungshärtbaren Gemischen.Radical sites are generated on the substrate, for example by discharge or radiation, the organic photoinitiators with at least one ethylenically unsaturated group are applied to the substrate and are allowed to react there with the radical sites generated, the substrate thus precoated with at least one ethylenically unsaturated monomer or Oligomers are coated and cured by means of UV / VIS radiation and a metal, semimetal or metal oxide is deposited from the gas phase in the presence of UV light. However, WO 00/24527 gives no technical teaching for the production of such photoinitiators of the phosphine oxide type and gives no indication of the reduction in migration when using such photoinitiators in radiation-curable mixtures.
J.H. de Groot et al . beschreiben in Polymeric Materials: Science & Engineering, 2001, 85, 53, einbaubare vinylfunktionalisierte Phosphinoxide, die an den aromatischen Gruppen eine Vinylgruppe tragen. Diese Verbindungen sind jedoch technisch nicht in großen Mengen produzierbar.J.H. de Groot et al. describe in Polymeric Materials: Science & Engineering, 2001, 85, 53, incorporable vinyl-functionalized phosphine oxides which carry a vinyl group on the aromatic groups. However, these compounds cannot be produced in large quantities industrially.
JP-A 08-167172 nennt Pivaloylphenylphosphinsäurevinylester und (Meth) acryloylphenylphosphinsäuremethylester als Photopolymerisationsinitiatoren in strahlungshärtbaren Klebstoffen.JP-A 08-167172 mentions vinyl pivaloylphenylphosphinate and methyl (meth) acryloylphenylphosphinate as photopolymerization initiators in radiation-curable adhesives.
JP-A 08-167172 erkennt jedoch nicht die geringere Migrationsten- denz solcher Phosphinoxide und gibt keinen Hinweis auf deren Herstellung.However, JP-A 08-167172 does not recognize the lower tendency of such phosphine oxides to migrate and gives no indication of their production.
Aufgabe der vorliegenden Erfindung war es, einbaubare Photoinitiatoren zu entwickeln, die eine geringere Migrationstendenz aufweisen als die herkömmlichen Photoinitiatoren vom Phosphinoxid- Typ, jedoch eine ähnliche Reaktivität aufweisen.The object of the present invention was to develop build-in photoinitiators which have a lower tendency to migrate than the conventional photoinitiators of the phosphine oxide type, but have a similar reactivity.
Die Aufgabe wurde gelöst durch Acyl- oder Bisacylphosphinderivate gemäß Formel (I) , zThe object was achieved by acyl or bisacylphosphine derivatives according to formula (I), e.g.
Figure imgf000004_0001
worin
Figure imgf000004_0001
wherein
R1, R2 Ci - Ci8~Alkyl, gegebenenfalls durch ein oder mehrereR 1 , R 2 Ci - Ci 8 ~ alkyl, optionally by one or more
Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubstituierte Iminogruppen unterbrochenes C2 - Cis-Alkyl, C2 - Ciβ-Alkenyl, C6 - Cι -Aryl, C5 - Cι2-Cycloalkyl oder einen fünf- bis sechs- gliedrigen, Sauerstoff-, Stickstoff- und/oder Schwefelatome aufweisenden Heterocyclus, wobei die genannten Reste jeweils durch Aryl , Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiert sein können, R2 ferner gegebenenfalls durch Aryl, Alkyl, Aryloxy, Alky- loxy, Heteroatome und/oder Heterocyclen substituiertes Ci - Cis-Alkoxy oder R1-(C=Y)-,Oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted C 2 - cis alkyl, C 2 - Ciβ-alkenyl, C 6 - Cι-aryl, C 5 - Cι 2 cycloalkyl or a five to six-membered heterocycle containing oxygen, nitrogen and / or sulfur atoms, where the radicals mentioned can each be substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, R 2 also optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles Ci - Cis-alkoxy or R 1 - (C = Y) -,
Y 0, S, NR3, N-OR3 oder N-NR3R4,Y 0, S, NR 3 , N-OR 3 or N-NR 3 R 4 ,
Z 0, S, NR3, N-OR3, N-NR3R4 oder ein freies Elektronenpaar,Z 0, S, NR 3 , N-OR 3 , N-NR 3 R 4 or a free electron pair,
R3 Wasserstoff, Ci bis C4-Alkyl, S03H, Phenyl oder Acetyl,R 3 is hydrogen, Ci to C 4 alkyl, S0 3 H, phenyl or acetyl,
R4 Wasserstoff, Ci bis C -Alkyl, COOR3 oder gegebenenfalls durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/ oder Heterocyclen substituiertes C6 - Cι -Aryl oder Aryl- sulfonyl,R 4 is hydrogen, C 1 to C -alkyl, COOR 3 or C 6 -C 8 -aryl or arylsulfonyl which is optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles,
X einen n-fach mit Gruppen RG substituierten Spacer,X is a spacer substituted n times with groups RG,
RG eine radikalisch oder kationisch polymerisierbare Gruppe oder eine Gruppe, die in Wechselwirkung mit dem sich bil- denden Polymer treten kann undRG is a radical or cationically polymerizable group or a group which can interact with the polymer being formed and
n eine natürliche Zahl von 1 bis 10 undn is a natural number from 1 to 10 and
bedeuten.mean.
X kann weiterhin unsubstituiertes oder mit Halogen, Ci-Cs-Alkyl, C2-Cs-Alkenyl, Carboxy, Carboxy-Ci-Cs-Alkyl , Cι-C2o~Acyl, Ci-Cs-Al- koxy, C6-Cι -Aryl, Hydroxyl, hydroxysubstituiertem Ci-Cβ-Alkyl oder n-fach von Gruppen RG substituiertes C6-Cι2-Arylen, C3-Cι -Cy- cloalkylen, Cι-C2fj-Alkylen oder durch ein- oder mehrere Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubstituierte Iminogruppen und/oder durch eine oder mehrere -(CO)-, -0(C0)0-, -(NH)(CO)0-, -0(CO)(NH)-, -0(C0)- oder - (CO) O-Gruppen unterbrochenes C2-C o-Alkylen bedeuten.X can also be unsubstituted or halogen, Ci-Cs-alkyl, C 2 -Cs-alkenyl, carboxy, carboxy-Ci-Cs-alkyl, -C-C 2 o ~ acyl, Ci-Cs-alkoxy, C 6 - -C aryl, hydroxyl, hydroxy-substituted Ci-Cβ-alkyl or n-fold substituted by groups RG C 6 -Cι 2 -arylene, C 3 -Cι -cycloalkylene, Cι-C 2f j -alkylene or by one or more Oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups and / or by one or more - (CO) -, -0 (C0) 0-, - (NH) (CO) 0-, -0 ( CO) (NH) -, -0 (C0) - or - (CO) O groups are interrupted C 2 -C o-alkylene.
Radikalisch polymerisierbare Gruppen sind beispielsweise isolierte ethylenisch ungesättigte Gruppen, konjugierte ungesättigte Gruppen, vinylaromatische Gruppen, vinyl- und vinylidenchloridi- sche Gruppen, N-Vinylamide, Vinylpyrrolidone, Vinyllactame, Viny- lester, (Meth) acrylester oder Acrylnitrile.Radically polymerizable groups are, for example, isolated ethylenically unsaturated groups, conjugated unsaturated groups, vinyl aromatic groups, vinyl and vinylidene chloride groups, N-vinyl amides, vinyl pyrrolidones, vinyl lactams, vinyl esters, (meth) acrylic esters or acrylonitriles.
Kationisch polymerisierbare Gruppen sind beispielsweise Isobuty- leneinheiten oder Vinylether.Cationically polymerizable groups are, for example, isobutylene units or vinyl ethers.
Darin bedeuten gegebenenfalls durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiertes Ci - Cι8-Alkyl beispielsweise Methyl, Ethyl , Propyl , Isopropyl, n-Butyl , sec-Butyl, tert.-Bu- tyl, Pentyl, Hexyl, Heptyl, Octyl, 2-Etylhexyl, 2 , 4 , 4-Trimethyl- 5 pentyl, Decyl, Dodecyl , Tetradecyl, Hetadecyl, Octadecyl, 1,1-Di- methylpropyl , 1, 1-Dimethylbutyl, 1, 1, 3 , 3-Tetramethylbutyl, Ben- zyl, 1-Phenylethyl, 2-Phenylethyl , α, α-Dimethylbenzyl , Benzhy- dryl , p-Tolylmethyl , 1- (p-Butylphenyl ) -ethyl , p-Chlorbenzyl , 2 , 4-Dichlorbenzyl, p-Methoxybenzyl , m-Ethoxybenzyl , 2-Cyanoethyl ,Mean in it C 1 -C 8 alkyl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, Heptyl, octyl, 2-ethylhexyl, 2, 4, 4-trimethyl-5-pentyl, decyl, dodecyl, tetradecyl, hetadecyl, octadecyl, 1,1-dimethylpropyl, 1, 1-dimethylbutyl, 1, 1, 3, 3 -Tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α, α-dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butylphenyl) -ethyl, p-chlorobenzyl, 2, 4-dichlorobenzyl, p Methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl,
10 2-Cyanopropyl, 2-Methoxycarbonethyl , 2-Ethoxycarbonylethyl , 2-Bu- toxycarbonylpropyl , 1 , 2-Di- (methoxycarbonyl) -ethyl , 2-Methoxye- thyl, 2-Ethoxyethyl, 2-Butoxyethyl , Diethoxymethyl , Diethoxye- thyl, l,3-Dioxolan-2-yl, 1 , 3-Dioxan-2-yl , 2-Methyl-l, 3-dioxo- lan-2-yl, 4-Methyl-l, 3-dioxolan-2-yl , 2-Isopropoxyethyl, 2-Buto-10 2-cyanopropyl, 2-methoxycarbonethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1, 2-di- (methoxycarbonyl) -ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl , l, 3-dioxolan-2-yl, 1, 3-dioxan-2-yl, 2-methyl-l, 3-dioxolan-2-yl, 4-methyl-l, 3-dioxolan-2-yl , 2-isopropoxyethyl, 2-buto-
15 xypropyl, 2-Octyloxyethyl, Chlormethyl, 2-Chlorethyl, Trichlorme- thyl, Trifluormethyl, 1, l-Dimethyl-2-chlorethyl, 2-Methoxyisopropyl , 2-Ethoxyethyl, Butylthiomethyl, 2-Dodecylthioethyl , 2-Phe- nylthioethyl, 2 , 2 , 2-Trifluorethyl , 2-Hydroxyethyl , 2-Hydroxypro- pyl, 3-Hydroxypropy1 , 4-Hydroxybutyl , 6-Hydroxyhexyl , 2-Aminoe-15 xypropyl, 2-octyloxyethyl, chloromethyl, 2-chloroethyl, trichloromethyl, trifluoromethyl, 1, l-dimethyl-2-chloroethyl, 2-methoxyisopropyl, 2-ethoxyethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 2nd , 2, 2-trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropy1, 4-hydroxybutyl, 6-hydroxyhexyl, 2-amino-
20 thyl, 2-Aminopropyl, 3-Aminopropyl , 4-Aminobutyl , 6-Aminohexyl , 2-Methylaminoethyl, 2-Methylaminopropyl , 3-Methylaminopropyl , 4-Methylaminobutyl, 6-Methylaminohexyl , 2-Dimethylaminoethyl, 2-Dimethylaminopropyl, 3-Dimethylaminopropyl , 4-Dimethylaminobu- tyl, 6-Dimethylaminohexyl, 2-Hydroxy-2 , 2-dimethylethyl, 2-Pheno-20 thyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl , 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2, 2-dimethylethyl, 2-pheno-
25 xyethyl, 2-Phenoxypropyl , 3-Phenoxypropyl , 4-Phenoxybutyl, 6-Phe- noxyhexyl, 2-Methoxyethyl, 2-Methoxypropyl , 3-Methoxypropyl, 4-Methoxybutyl, 6-Methoxyhexyl , 2-Ethoxyethyl, 2-Ethoxypropyl , 3-Ethoxypropyl, 4-Ethoxybutyl oder 6-Ethoxyhexyl,25 xyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3 -Ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl,
30 gegebenenfalls durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiertes Ci - Ci8-Alkoxy beispielsweise Methoxy, Ethoxy, n-Propyloxy, iso-Propyloxy, n-Butyloxy, iso-Butyloxy, sek. -Butyloxy, tert . -Butyloxy, 6-Hydroxy-l, 4-dioxo- hexyl, 9-Hydroxy-l, 4, 7-trioxononyl, 12-Hydroxy-l , 4 , 7 , 10-tetraoxo-30 optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles Ci - Ci 8 alkoxy, for example methoxy, ethoxy, n-propyloxy, iso-propyloxy, n-butyloxy, iso-butyloxy, sec. -Butyloxy, tert. -Butyloxy, 6-hydroxy-l, 4-dioxo-hexyl, 9-hydroxy-l, 4, 7-trioxononyl, 12-hydroxy-l, 4, 7, 10-tetraoxo-
35 dodecyl, 6-Methoxy-l, 4-dioxohexyl, 9-Methoxy-l, 4 , 7-trioxononyl, 12-Methoxy-l ,4,7, 10-tetraoxododecyl , 6-Ethoxy-l , 4-dioxohexyl , 9-Ethoxy-l, 4, 7-trioxononyl , 12-Ethoxy-l, 4,7, 10-tetraoxododecyl , 8-Hydroxy-l, 5-dioxooctyl, 12-Hydroxy-l , 5 , 9-trioxooctyl, 16-Hy- droxy-1 ,5,9, 13-tetraoxohexadecyl , 8-Methoxy-l , 5-dioxooctyl ,35 dodecyl, 6-methoxy-l, 4-dioxohexyl, 9-methoxy-l, 4, 7-trioxononyl, 12-methoxy-l, 4,7, 10-tetraoxododecyl, 6-ethoxy-l, 4-dioxohexyl, 9 -Ethoxy-l, 4, 7-trioxononyl, 12-ethoxy-l, 4,7, 10-tetraoxododecyl, 8-hydroxy-l, 5-dioxooctyl, 12-hydroxy-l, 5, 9-trioxooctyl, 16-hy droxy-1, 5,9, 13-tetraoxohexadecyl, 8-methoxy-l, 5-dioxooctyl,
40 12-Methoxy-l, 5 , 9-trioxooctyl , 16-Methoxy-l , 5,9, 13-tetraoxohexade- cyl, 8-Ethoxy-l , 5-dioxooctyl, 12-Ethoxy-l , 5 , 9-trioxooctyl , 16-Ethoxy-l, 5,9, 13-tetraoxohexadecyl , 10-Hydroxy-l , 6-dioxodecyl , 15-Hydroxy-l , 6 , 11-trioxopentadecyl , 10-Methoxy-l , 6-dioxodecyl , 15-Methoxy-l, 6, 11-trioxopentadecyl , 10-Ethoxy-l, 6-dioxodecyl oder40 12-methoxy-l, 5, 9-trioxooctyl, 16-methoxy-l, 5.9, 13-tetraoxohexadecyl, 8-ethoxy-l, 5-dioxooctyl, 12-ethoxy-l, 5, 9-trioxooctyl , 16-ethoxy-l, 5,9, 13-tetraoxohexadecyl, 10-hydroxy-l, 6-dioxodecyl, 15-hydroxy-l, 6, 11-trioxopentadecyl, 10-methoxy-l, 6-dioxodecyl, 15-methoxy -l, 6, 11-trioxopentadecyl, 10-ethoxy-l, 6-dioxodecyl or
45 15-Ethoxy-l , 6 , 11-trioxopentadecyl , gegebenenfalls durch ein oder mehrere Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubstituierte Iminogruppen unterbrochenes C - Cis-Alkyl beispielsweise 5-Hydroxy-3-oxa-pentyl, 8-Hydroxy-3 , 6-dioxa-octyl, 11-Hy- droxy-3 , 6, 9-trioxa-undecyl, 7-Hydroxy-4-oxa-heptyl, 11-Hy- droxy-4, 8-dioxa-undecyl, 15-Hydroxy-4, 8, 12-trioxa-pentadecyl, 9-Hydroxy-5-oxa-nonyl, 14-Hydroxy-5, 10-oxa-tetradecyl, 5-Me- thoxy-3-oxa-pentyl, 8-Methoxy-3 , 6-dioxa-octyl , 11-Me- thoxy-3 , 6 , 9-trioxa-undecyl , 7-Methoxy-4-oxa-heptyl , 11-Me- thoxy-4 , 8-dioxa-undecyl , 15-Methoxy-4 , 8 , 12-trioxa-pentadecyl , 9-Methoxy-5-oxa-nonyl , 14-Methoxy-5 , 10-oxa-tetradecyl , 5-Ethoxy-3-oxa-pentyl, 8-Ethoxy-3, 6-dioxa-octyl, ll-Ethoxy-3, 6, 9-trioxa-undecyl, 7-Ethoxy-4-oxa-heptyl, ll-Ethoxy-4 , 8-dioxa-undecyl , 15-Ethoxy-4 , 8 , 12-trioxa-pentadecyl , 9-Ethoxy-5-oxa-nonyl oder 14-Ethoxy-5, 10-oxa-tetradecyl .45 15-ethoxy-l, 6, 11-trioxopentadecyl, C - Cis-alkyl optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, for example 5-hydroxy-3-oxapentyl, 8-hydroxy-3, 6-dioxa-octyl, 11-hydroxy-3, 6, 9-trioxa-undecyl, 7-hydroxy-4-oxa-heptyl, 11-hydroxy-4, 8-dioxa-undecyl, 15-hydroxy-4, 8, 12- trioxa-pentadecyl, 9-hydroxy-5-oxa-nonyl, 14-hydroxy-5, 10-oxa-tetradecyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3, 6-dioxa-octyl, 11-methoxy-3, 6, 9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 11-methoxy-4, 8-dioxa-undecyl, 15-methoxy-4, 8, 12- trioxa-pentadecyl, 9-methoxy-5-oxa-nonyl, 14-methoxy-5, 10-oxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3, 6-dioxa-octyl, ll- Ethoxy-3, 6, 9-trioxa-undecyl, 7-ethoxy-4-oxa-heptyl, ll-ethoxy-4, 8-dioxa-undecyl, 15-ethoxy-4, 8, 12-trioxa-pentadecyl, 9- Ethoxy-5-oxa-nonyl or 14-ethoxy-5, 10-oxa-tetradecyl.
Die Anzahl der Sauerstoff- und/oder Schwefelatome und/oder Iminogruppen ist nicht beschränkt. In der Regel beträgt sie nicht mehr als 5 in dem Rest, bevorzugt nicht mehr als 4 und ganz besonders bevorzugt nicht mehr als 3.The number of oxygen and / or sulfur atoms and / or imino groups is not restricted. As a rule it is not more than 5 in the rest, preferably not more than 4 and very particularly preferably not more than 3.
Weiterhin befinden sich zwischen zwei Heteroatomen in der Regel mindestens ein Kohlenstoffatom, bevorzugt mindestens zwei.Furthermore, there are generally at least one carbon atom, preferably at least two, between two heteroatoms.
Substituierte und unsubstituierte Iminogruppen können beispielsweise Imino-, Methyli ino-, iso-Propylimino, n-Butylimino oder tert-Butylimino sein.Substituted and unsubstituted imino groups can be, for example, imino, methyli ino, iso-propylimino, n-butylimino or tert-butylimino.
Weiterhin bedeutetAlso means
gegebenenfalls durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiertes C2 - Cis-Alkenyl beispielsweise Vinyl, 1-Propenyl, Allyl, Methallyl, 1, 1-Dimethylallyl , 2-Butenyl, 2-Hexenyl, Octenyl, Undecenyl, Dodecenyl, Octadecenyl, 2-Phenylvinyl, 2-Methoxyvinyl , 2-Ethoxyvinyl , 2-Methoxyallyl , 3-Methoxyallyl, 2-Ethoxyallyl , 3-Ethoxyallyl oder 1- oder 2-Chlorvinyl,C 2 - cis alkenyl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example vinyl, 1-propenyl, allyl, methallyl, 1, 1-dimethylallyl, 2-butenyl, 2-hexenyl, octenyl, undecenyl , Dodecenyl, octadecenyl, 2-phenylvinyl, 2-methoxyvinyl, 2-ethoxyvinyl, 2-methoxyallyl, 3-methoxyallyl, 2-ethoxyallyl, 3-ethoxyallyl or 1- or 2-chlorovinyl,
gegebenenfalls durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiertes Ce - Cι -Aryl beispielsweise Phenyl, Tolyl, Xylyl , α-Naphthyl, ß-Naphthyl , 4-Diphenylyl , Chlorphenyl, Dichlorphenyl, Trichlorphenyl, Difluorphenyl, Me- thylphenyl, Dimethylphenyl , Trimethylphenyl , Ethylphenyl , Die- thylphenyl, iso-Propylphenyl , tert . -Butylphenyl , Dodecylphenyl , Methoxyphenyl, Dimethoxyphenyl, Ethoxyphenyl, Hexyloxyphenyl, Me- thylnaphthyl , Isopropylnaphthyl , Chlornaphthyl , Ethoxynaphthyl , 2 , 6-Dimethylphenyl , 2,4, 6-Trimethylphenyl , 2 , 6-Dimethoxyphenyl , 2, 6-Dichlorphenyl, 4-Brompheny1 , 2- oder 4-Nitrophenyl, 2,4- oder 2 , 6-Dinitrophenyl, 4-Dimethylaminophenyl, 4-Acetylphenyl, Metho- xyethylphenyl oder Ethoxymethylphenyl ,Ce - -C aryl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, Me- thylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert. -Butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2, 6-dimethylphenyl, 2,4, 6-trimethylphenyl, 2, 6-dimethoxyphenyl, 2, 6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl or ethoxymethylphenyl,
gegebenenfalls durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiertes C5 - Cι2-Cycloalkyl beispielsweise Cyclopentyl, Cyclohexyl, Cyclooctyl, Cyclododecyl, Methylcyclopentyl, Dimethylcyclopentyl, Methylcyclohexyl, Dime- thylcyclohexyl, Diethylcyclohexyl, Butylcyclohexyl, Methoxycyclo- hexyl, Dimethoxycyclohexyl, Diethoxycyclohexyl, Butylthiocyclohe- xyl, Chlorcyclohexyl, Dichlorcyclohexyl, Dichlorcyclopentyl sowie ein gesättigtes oder ungesättigtes bicyclisches System wie z.B. Norbornyl oder Norbornenyl,C 5 -C 2 -cycloalkyl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, methoxycyclohexyl, diethylcyclohexyl, Dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl,
ein fünf- bis sechsgliedriger, Sauerstoff-, Stickstoff- und/oder Schwefelatome aufweisender Heterocyclus beispielsweise Furyl , Thiophenyl, Pyrryl, Pyridyl, Indolyl, Benzoxazolyl, Dioxolyl, Dioxyl, Benzimidazolyl, Benzthiazolyl , Dimethylpyridyl, Methyl- chinolyl, Dimethylpyrryl, Methoxyfuryl , Dirnethoxypyridyl , Diflu- orpyridyl, Methylthiophenyl, Isopropylthiophenyl oder tert. -Butylthiophenyl ,a five- to six-membered heterocycle containing oxygen, nitrogen and / or sulfur atoms, for example furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrylidyl, dimethylpyrylidyl Difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert. -Butylthiophenyl,
Ci bis C4-Alkyl beispielsweise Methyl, Ethyl, Propyl, Isopropyl, n-Butyl , sec-Butyl oder tert . -Butyl undCi to C 4 alkyl, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert. -Butyl and
gegebenenfalls durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiertes C6 - Cι2-Aryl oder Arylsulfo- nyl beispielsweise Phenyl, 2, 6-Dinitrophenyl, 2 , 4-Dinitrophenyl, 2-Nitrophenyl, 4-Nitrophenyl, Formyl , Acetyl, Propionyl, Carba- moyl, Phenylsulfonyl oder 4-Methylphenylsulfonyl .optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles C 6 -C 2 aryl or arylsulfonyl, for example phenyl, 2, 6-dinitrophenyl, 2, 4-dinitrophenyl, 2-nitrophenyl, 4-nitrophenyl, Formyl, acetyl, propionyl, carbamoyl, phenylsulfonyl or 4-methylphenylsulfonyl.
Die Anzahl der Substituenten in den angegebenen Resten ist nicht beschränkt. In der Regel beträgt sie bei Resten mit ein bis drei Kohlenstoffatomen bis zu 3 Substituenten, bevorzugt bis zu 2 und besonders bevorzugt bis zu einem. Bei Resten mit vier bis sechs Kohlenstoffatomen beträgt sie in der Regel bis zu 4 Substituenten, bevorzugt bis zu 3 und besonders bevorzugt bis zu einem. Bei Resten mit mehr als sieben Kohlenstoffatomen beträgt sie in der Regel bis zu 6 Substituenten, bevorzugt bis zu 4 und besonders bevorzugt bis zu zwei.The number of substituents in the stated radicals is not restricted. As a rule, in the case of radicals having one to three carbon atoms, it is up to 3 substituents, preferably up to 2 and particularly preferably up to one. In the case of radicals with four to six carbon atoms, it is generally up to 4 substituents, preferably up to 3 and particularly preferably up to one. In the case of radicals with more than seven carbon atoms, it is generally up to 6 substituents, preferably up to 4 and particularly preferably up to two.
X kann beispielsweise sein 1,2-Ethylen, 1 , 2-Propylen, 1,3-Propy- len, 1,4-Butylen, 1,6-Hexylen, 2-Methyl-l , 3-Propylen, 2-Ethyl-l,3-Propylen, 2 , 2-Dimethyl-l , 3-Propylen, 2,2-Dime- thyl-l,4-butylen, 1-Oxa-l , 3-propylen, 1 , 4-Dioxa-l, 6-hexylen,X can be, for example, 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene, 1,6-hexylene, 2-methyl-1,3-propylene, 2-ethyl- l, 3-propylene, 2, 2-dimethyl-l, 3-propylene, 2,2-dimethyl-l, 4-butylene, 1-oxa-l, 3-propylene, 1, 4-dioxa-l, 6-hexylene,
1,4, 7-Trioxa-l, 9-nonylen, 1-Oxa-l , 4-butylen, 1,5-Dioxa-l, 8-octy- len, 1-Oxa-l, 5-pentylen, 1-Oxa-l, 7-heptylen, 1 , 6-Dioxa-l , 10-decy- len, l-Oxa-3-methyl-l,3-propylen, l-Oxa-3-methyl-l, 4-butylen, l-Oxa-3, 3-dimethyl-l,4-butylen, l-Oxa-3 , 3-dimethyl-l, 5-pentylen, 1, 4-Dioxa-3 , 6-dimethyl-l, 6-hexylen, l-Oxa-2-methyl-l, 3-propylen, 1, 4-Dioxa-2, 5-dimethyl-l, 6-hexylen, 1-Oxa-l, 5-pent-3-enylen, 1-Oxa-l, 5-pent-3-inylen, 1,1-, 1,2-, 1,3- oder 1, 4-Cyclohexylen, 1,2- oder 1, 3-Cyclopentylen, 1,2-, 1,3- oder 1, 4-Phenylen, 4, 4 ' -Biphenylen, 1 , 4-Diaza-l , 4-butylen, 1-Aza-l, 3-propylen, 1,4, 7-Triaza-l, 7-heptylen, 1, 4-Diaza-l, 6-hexylen, 1, 4-Diaza-7-oxa-l, 7-heptylen, 4, 7-Diaza-l-oxa-l , 7-heptylen, 4-Aza-l-oxa-l, 6-hexylen, l-Aza-4-oxa-l , 4-butylen, 1-Aza-l, 3-pro- pylen, 4-Aza-l-oxa-l , 4-butylen, 4-Aza-l , 7-dioxa-l , 7-heptylen, 4-Aza-l-oxa-4-methyl-l, 6-hexylen, 4-Aza-l, 7-dioxa-4-me- thyl-1, 7-heptylen, 4-Aza-l, 7-dioxa-4- (2 ' -hydroxyethyl) -1, 7-hepty- len, 4-Aza-l-oxa- (2 '-hydroxyethyl) -1, 6-hexylen oder 1, 4-Piperazi- nylen.1,4, 7-trioxa-l, 9-nonylene, 1-oxa-l, 4-butylene, 1,5-dioxa-l, 8-octylene, 1-oxa-l, 5-pentylene, 1- Oxa-l, 7-heptylene, 1, 6-dioxa-l, 10-decy- len, l-oxa-3-methyl-l, 3-propylene, l-oxa-3-methyl-l, 4-butylene, l-oxa-3, 3-dimethyl-l, 4-butylene, l-oxa- 3, 3-dimethyl-l, 5-pentylene, 1, 4-dioxa-3, 6-dimethyl-l, 6-hexylene, l-oxa-2-methyl-l, 3-propylene, 1, 4-dioxa- 2, 5-dimethyl-l, 6-hexylene, 1-oxa-l, 5-pent-3-enylene, 1-oxa-l, 5-pent-3-inylene, 1,1-, 1,2-, 1,3- or 1,4-cyclohexylene, 1,2- or 1,3-cyclopentylene, 1,2-, 1,3- or 1,4-phenylene, 4,4'-biphenylene, 1,4-diaza -l, 4-butylene, 1-aza-l, 3-propylene, 1,4, 7-triaza-l, 7-heptylene, 1, 4-diaza-l, 6-hexylene, 1, 4-diaza-7 -oxa-l, 7-heptylene, 4, 7-diaza-l-oxa-l, 7-heptylene, 4-aza-l-oxa-l, 6-hexylene, l-aza-4-oxa-l, 4 -butylene, 1-aza-l, 3-propylene, 4-aza-l-oxa-l, 4-butylene, 4-aza-l, 7-dioxa-l, 7-heptylene, 4-aza-l -oxa-4-methyl-l, 6-hexylene, 4-aza-l, 7-dioxa-4-methyl-1, 7-heptylene, 4-aza-l, 7-dioxa-4- (2 ' -hydroxyethyl) -1, 7-heptylene, 4-aza-l-oxa- (2 '-hydroxyethyl) -1, 6-hexylene or 1, 4-piperazinyls.
Weiterhin kann X für eine Spacergruppe stehen, wie sie im wesentlichen in WO 00/24527 beschrieben ist. Demnach kann X fürX can furthermore represent a spacer group, as is essentially described in WO 00/24527. Accordingly, X can be used for
-Zl-[(Aι)a-Z2]c-[(A2)b-Z3]d -Zl - [(Aι) a -Z 2 ] c - [(A 2 ) b -Z 3 ] d
stehen, worinstand in what
Z1, Z2, und Z3 jeweils unabhängig voneinander für eine Einfachbin- d ng, -0-, -S-, -N(R8)-, -(CO)-, -(CO)O-, -(CO)N(R8)-, -O-(CO)-, -N(R8)-(CO)- oder -N(R8) - (CO) 0- stehen,Z 1 , Z 2 , and Z 3 each independently for a single bond, -0-, -S-, -N (R 8 ) -, - (CO) -, - (CO) O-, - ( CO) N (R 8 ) -, -O- (CO) -, -N (R 8 ) - (CO) - or -N (R 8 ) - (CO) 0-,
x und A unabhängig voneinander Ci - C -Alkylen, C3 - Cχ2-Cycloal- kylen, Phenylen, Phenylen-Ci - C -Alkylen oder Ci - C -Alkylen- Phenylen-Ci - C4-Alkylen bedeuten undx and A independently of one another are Ci - C alkylene, C 3 - Cχ 2 cycloalkylene, phenylene, phenylene-Ci - C -alkylene or Ci - C -alkylene-phenylene-Ci - C 4 -alkylene and
a,b,c,d unabhängig voneinander für die Zahlen 0 bis 4 stehen.a, b, c, d independently of one another represent the numbers 0 to 4.
R8 ist darin Wasserstoff, Ci bis Cis-Alkyl oder Phenyl.R 8 is hydrogen, Ci to Cis-alkyl or phenyl.
Darin bedeuten Ci - C -Alkylen lineares oder verzweigtes Alkylen, z.B. Methylen, 1,2-Ethylen, 1,2- oder 1 , 3-Propylen, 1,2-, 1,3- oder 1,4-Butylen, 1, 1-Dimethyl-l, 2-ethylen oder 1,2-Dime- thyl-1 , 2-ethylen,Ci - C alkylene therein denotes linear or branched alkylene, e.g. Methylene, 1,2-ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 1,1-dimethyl-1,2-ethylene or 1,2 -Dime- 1, 2-ethylene,
C - Cι2-Cycloalkylen beispielsweise Cyclopropylen, Cyclopentylen,C 1 -C 2 -cycloalkylene, for example cyclopropylene, cyclopentylene,
Cyclohexylen, Cyclooctylen, Cyclododecylen, Phenylen-Ci - C -Alkylen steht für Phenylen, welches in einer Position des aromatischen Ringes mit Ci - C -Alkylen substituiert ist, beispielsweise 1 ' , 4-Toluylen oder 1 ' , 1 ' -Dimethyl-1' , 4-Toluy- len,Cyclohexylene, cyclooctylene, cyclododecylene, Phenylene-Ci-C-alkylene stands for phenylene which is substituted in one position of the aromatic ring with Ci-C-alkylene, for example 1 ', 4-tolylene or 1', 1 '-dimethyl-1', 4-Toluy- len,
Ci - C -Alkylen-Phenylen-Cι - C -Alkylen steht für Phenylen, welches in zwei Positionen des aromatischen Ringes mit Ci - C -Alky- len substituiert ist, beispielsweise 2 , 4-Dimethylphenyl-l ' , 1 ' '-en oder 1 ' , 1 ' -Dimethyl-2 , 4-Dimethylphenyl-l ' , 1 ' ' -en .Ci - C -alkylene-phenylene-Cι-C -alkylene stands for phenylene, which is substituted in two positions of the aromatic ring with Ci - C -alkylene, for example 2, 4-dimethylphenyl-l ', 1' '-en or 1 ', 1' -dimethyl-2, 4-dimethylphenyl-l ', 1 "' s.
Unter diesen sind solche Verbindungen bevorzugt, in denen die Spacergruppe X fürAmong these, preference is given to those compounds in which the spacer group X is for
-Zi-[(CH2)a- Z ]c-[( CH2)b- Z ]d ,-Z i - [(CH 2 ) a - Z] c - [(CH 2 ) b - Z] d ,
worin Z1, Z2, Z3, a, b, c und d wie vorstehend definiert sind.wherein Z 1 , Z 2 , Z 3 , a, b, c and d are as defined above.
RG bedeutet einen Rest der FormelRG means a residue of the formula
Figure imgf000010_0001
Figure imgf000010_0001
oder 2-Vinylphen-l-yl, 3-Vinylphen-l-yl oder 3-Vinylphen-l-yl .or 2-vinylphen-l-yl, 3-vinylphen-l-yl or 3-vinylphen-l-yl.
R5, R6, R7 bedeuten darin Ci - Cis-Alkyl, gegebenenfalls durch ein oder mehrere Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubstituierte Iminogruppen unterbro- chenes C2 - Cis-Alkyl, Ci - Cia-Alkoxy, C2 - Cis-Alkenyl, C6 - Cι -Aryl, C5 - Cι2-Cycloalkyl oder einen fünf- bis sechsgliedri- gen, Sauerstoff-, Stickstoff- und/oder Schwefelatome aufweisenden Heterocyclus, wobei die genannten Reste jeweils durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substi- tuiert sein können,R 5 , R 6 , R 7 therein mean C 1 -C 4 -alkyl, optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, C 2 -C 3 -alkyl, Ci-Cia -Alkoxy, C 2 - cis-alkenyl, C 6 - -CC aryl, C 5 - C 2 cycloalkyl or a five- to six-membered heterocycle having oxygen, nitrogen and / or sulfur atoms, the radicals mentioned in each case can be substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles,
RG kann beispielsweise Vinyl, Vinyloxy, 1-Propen-l-yl, 1-Pro- pen-2-yl, 2-Buten-2-yl, 3-Methyl-2-Buten-2-yl, 2-Vinylphen-l-yl , 3-Vinylphen-l-yl, 3-Vinylphen-l-yl, 2-Phenylethen-l-yl, 2-(4-Me- thoxyphenyl) -ethen-1-yl, Acryl, Methacryl, Crotonyl, Acryloxy, Acrylamido, Methacryloxy oder Crotonyloxy sein.RG can, for example, vinyl, vinyloxy, 1-propen-1-yl, 1-propen-2-yl, 2-buten-2-yl, 3-methyl-2-buten-2-yl, 2-vinylphen-1 -yl, 3-vinylphen-l-yl, 3-vinylphen-l-yl, 2-phenylethen-l-yl, 2- (4-methoxyphenyl) ethen-1-yl, acrylic, methacrylic, crotonyl, acryloxy , Acrylamido, methacryloxy or crotonyloxy.
Weiterhin kann RG eine GruppeFurthermore, RG can be a group
-N+R9 3, -OR9, -SR9, C00" oder C00R9 bedeuten, worin-N + R 9 3 , -OR 9 , -SR 9 , C00 "or C00R 9 mean what
R9 jeweils gleich oder unterschiedlich Wasserstoff oder Cι~C-Al- kyl , beispielsweise Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, seJ-Butyl oder tert. -Butyl, sein kann.R 9 each identically or differently hydrogen or -CC-alkyl, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, seJ-butyl or tert. -Butyl, can be.
Weiterhin können die Gruppen X-RGn beispielsweise sein,The groups X-RG n can furthermore be, for example,
/ A 4 \ z4 A3 N z5/ A 4 \ z 4 A 3 N z 5
A 5 A 5
-Z4-A3-Z5-A4-Z7 oder-Z 4 -A 3 -Z 5 -A 4 -Z 7 or
-Z4-[A3-Z5]e-R9.-Z 4 - [A 3 -Z5] e -R 9 .
Solche XRGn können beispielsweise sein 2-Dimethylaminoethoxy, 2-Aminoethoxy, l-Aza-3-aminoprop-l-yl, 1 , 4-Diaza-6-aminohexyl , 4-Aza-l-oxa-6-aminohexyl, 4-Aza-l-oxa-6-hydroxyhexyl , l-Aza-3-hy- droxy-1- (2 'hydroxyethyl) -propyl, Piperazin-1-yl, 4-Methyl-pipera- zin-l-yl oder 2 ' -Piperazinoethoxy.Such XRG n can be, for example, 2-dimethylaminoethoxy, 2-aminoethoxy, l-aza-3-aminoprop-l-yl, 1,4-diaza-6-aminohexyl, 4-aza-l-oxa-6-aminohexyl, 4- Aza-l-oxa-6-hydroxyhexyl, l-aza-3-hydroxy-1- (2 'hydroxyethyl) propyl, piperazin-1-yl, 4-methyl-piperazine-l-yl or 2' -Piperazinoethoxy.
Weiterhin kann X beispielsweise seinX can also be, for example
Figure imgf000011_0001
Figure imgf000011_0001
Figure imgf000011_0002
Figure imgf000011_0002
Figure imgf000011_0003
Figure imgf000011_0003
Wenn XRGn mehrere Gruppen RG trägt, so kann es beispielsweise sein
Figure imgf000012_0001
worin jeweils unabhängig voneinander sein können Z4, Z5, Z6 Einfachbindung, O, S, NH, NR10, CH2, CHR10, CR10 2, -(CO)-, -(CO)O-, -(CO)N(R10)-, -O-(CO)-, -N (R10 ) - (CO ) - oder -N(R10)-(CO)O-,If XRG n bears several RG groups, it can be, for example
Figure imgf000012_0001
where Z 4 , Z 5 , Z 6 single bond, O, S, NH, NR 10 , CH 2 , CHR 10 , CR 10 2 , - (CO) -, - (CO) O-, - ( CO) N (R 10 ) -, -O- (CO) -, -N (R 10 ) - (CO) - or -N (R 10 ) - (CO) O-,
Z7 -OH, -SH, -NR10 2,Z 7 -OH, -SH, -NR 10 2 ,
A , A4, A5 Einfachbindung, Ci - C4-Alkylen, C3 - Cι2-Cycloalkylen, Phenylen, Phenylen-Ci - C4-Alkylen oder Ci - C4-Alkylen-Phenylen- C - C4-Alkylen,A, A 4 , A 5 single bond, Ci - C 4 alkylene, C 3 - C 2 cycloalkylene, phenylene, phenylene-Ci - C 4 alkylene or Ci - C 4 alkylene-phenylene-C - C 4 alkylene .
e eine ganze Zahl zwischen 0 und 20 unde an integer between 0 and 20 and
R10 jeweils unabhängig voneinander Wasserstoff, Cι-C4-Alkyl, Cι-C4-Alkoxy, Hydroxy, Hydroxy-Cι-C4-Alkyl , Carboxyl , Cι-C4-Acyl, Carboxy-Cι-C4-Alkyl, C6-Cι2-Aryl, -O-RG, -CH2OH oder -CH20-RG.R 10 each independently of one another hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 alkoxy, hydroxy, hydroxy C 1 -C 4 alkyl, carboxyl, C 1 -C 4 -acyl, carboxy C 1 -C 4 alkyl, C 6 -Cι 2 aryl, -O-RG, -CH 2 OH or -CH 2 0-RG.
R1 ist bevorzugt Phenyl, Tolyl, Xylyl, α-Naphthyl, ß-Naphthyl, 2- 3- oder 4-Chlorphenyl, 2,6- oder 2 , 4-Dichlorphenyl , 2,4,6-Trich- lorphenyl, 2-, 3- oder 4-Methylphenyl, 2,6- oder 2 , -Dimethylphe- nyl, 2, 4, 6-Trimethylphenyl, 2-, 3- oder 4-Ethylphenyl, 2,6- oder 2, 4-Diethylphenyl, 2-, 3- oder 4-iso-Propylphenyl , 2-, 3- oder 4-tert.-Butylphenyl, 2-, 3- oder 4-Methoxyphenyl , 2,6- oder 2 , 4-Dimethoxyphenyl, 2,6- oder 2 , 4-Diethoxyphenyl , Methylnaph- 5 thyl , 2 , 6-Dimethylphenyl , 2,4, 6-Trimethylphenyl , 2 , 6-Dimethoxy- phenyl, 2 , 6-Dichlorphenyl, 4-Bromphenyl , 2- oder 4-Nitrophenyl, 2,4- oder 2 , 6-Dinitrophenyl, 4-Dimethylaminophenyl, 4-Acetylphe- nyl, Cyclopentyl, Cyclohexyl, 2 , 5-Dimethylcyclopentyl , 2,6-Dime- thylcyclohexyl , 2 , 6-Diethylcyclohexyl , 2 , 6-Dimethoxycyclohexyl , 10 2, 6-Diethoxycyclohexyl, 2 , 6-Dichlorcyclohexyl , 2 , 5-Dichlorcyclo- pentyl, 2- oder 3-Furyl, 2- oder 3-Thiophenyl , 2- oder 3-Pyrryl oder Dimethylpyrryl .R 1 is preferably phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 2- 3- or 4-chlorophenyl, 2,6- or 2, 4-dichlorophenyl, 2,4,6-trichlorophenyl, 2- , 3- or 4-methylphenyl, 2,6- or 2, -dimethylphe- nyl, 2, 4, 6-trimethylphenyl, 2-, 3- or 4-ethylphenyl, 2,6- or 2, 4-diethylphenyl, 2-, 3- or 4-iso-propylphenyl, 2-, 3- or 4 -tert.-butylphenyl, 2-, 3- or 4-methoxyphenyl, 2,6- or 2, 4-dimethoxyphenyl, 2,6- or 2, 4-diethoxyphenyl, methylnaph- 5 thyl, 2, 6-dimethylphenyl, 2 , 4, 6-trimethylphenyl, 2, 6-dimethoxyphenyl, 2, 6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2, 6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphe - nyl, cyclopentyl, cyclohexyl, 2, 5-dimethylcyclopentyl, 2,6-dimethylcyclohexyl, 2, 6-diethylcyclohexyl, 2, 6-dimethoxycyclohexyl, 10 2, 6-diethoxycyclohexyl, 2, 6-dichlorocyclohexyl, 2, 5- Dichlorocyclopentyl, 2- or 3-furyl, 2- or 3-thiophenyl, 2- or 3-pyrryl or dimethylpyrryl.
R1 ist besonders bevorzugt Phenyl, Tolyl, α-Naphthyl, ß-Naphthyl,R 1 is particularly preferably phenyl, tolyl, α-naphthyl, β-naphthyl,
15 2,6- oder 2 , 4-Dichlorphenyl, 2 , 4, 6-Trichlorphenyl, 2,6- oder15 2,6- or 2, 4-dichlorophenyl, 2, 4, 6-trichlorophenyl, 2,6- or
2,4-Dimethylphenyl, 2 , 4 , 6-Trimethylphenyl , 2,6- oder 2,4-Diethyl- phenyl, 2-iso-Propylphenyl, 2-tert . -Butylphenyl, 2,6- oder 2, 4-Dirnethoxyphenyl, 2,6- oder 2 , 4-Diethoxyphenyl, Methylnaph- thyl , 2 , 6-Dimethylphenyl , 2,4, 6-Trimethylphenyl , 2 , 6-Dimethoxy-2,4-dimethylphenyl, 2, 4, 6-trimethylphenyl, 2,6- or 2,4-diethylphenyl, 2-iso-propylphenyl, 2-tert. -Butylphenyl, 2,6- or 2, 4-dirthhoxyphenyl, 2,6- or 2, 4-diethoxyphenyl, methylnaphthyl, 2, 6-dimethylphenyl, 2,4, 6-trimethylphenyl, 2, 6-dimethoxy-
20 phenyl , 2 , 6-Dichlorphenyl , 2 , 6-Dinitrophenyl , 2 , 5-Dimethylcyclo- pentyl, 2 , 6-Dimethylcyclohexyl , 2 , 6-Diethylcyclohexyl, 2,6-Dime- thoxycyclohexyl , 2 , 6-Diethoxycyclohexyl , 2 , 6-Dichlorcyclohexyl , 2, 5-Dichlorcyclopentyl oder ortho-substituierte Phenyle, wie 2-Methylphenyl, 2-Methoxyphenyl oder 2-Chlorphenyl .20 phenyl, 2, 6-dichlorophenyl, 2, 6-dinitrophenyl, 2, 5-dimethylcyclopentyl, 2, 6-dimethylcyclohexyl, 2, 6-diethylcyclohexyl, 2,6-dimethoxycyclohexyl, 2, 6-diethoxycyclohexyl, 2 , 6-dichlorocyclohexyl, 2, 5-dichlorocyclopentyl or ortho-substituted phenyls, such as 2-methylphenyl, 2-methoxyphenyl or 2-chlorophenyl.
25 R1 ist ganz besonders bevorzugt Phenyl, 2-Methylphenyl, 2-Methoxy- phenyl , 2-Chlorphenyl , α-Naphthyl , 2 , 6-Dichlorphenyl , 2,4, 6-Trich- lorphenyl, 2 , 6-Dimethylphenyl, 2 , 4, 6-Trimethylphenyl , 2,6-Die- thylphenyl , 2 , 6-Dimethoxyphenyl , 2,6- Diethoxyphenyl , 2 , 6-Dime- thylphenyl, 2 , 4 , 6-Trimethylphenyl, 2 , 6-Dirnethoxyphenyl, 2,6-Dich-25 R 1 is very particularly preferably phenyl, 2-methylphenyl, 2-methoxyphenyl, 2-chlorophenyl, α-naphthyl, 2, 6-dichlorophenyl, 2,4, 6-trichlorophenyl, 2, 6-dimethylphenyl, 2 , 4, 6-trimethylphenyl, 2,6-diethylphenyl, 2, 6-dimethoxyphenyl, 2,6-diethoxyphenyl, 2, 6-dimethylphenyl, 2, 4, 6-trimethylphenyl, 2, 6-dimethoxyphenyl, 2nd , 6-dense
30 lorphenyl, 2 , 6-Dinitrophenyl, 2 , 6-Dimethylcyclohexyl , 2, 6-Diethylcyclohexyl , 2 , 6-Dimethoxycyclohexyl , 2 , 6-Diethoxycyclohexyl oder 2 , 6-Dichlorcyclohexyl .30 lorphenyl, 2,6-dinitrophenyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-dimethoxycyclohexyl, 2,6-diethoxycyclohexyl or 2,6-dichlorocyclohexyl.
R1 ist insbesondere Phenyl, 2 , 6-Dichlorphenyl, 2 , 4, 6-Trichlorphe- 35 nyl, 2, 6-Dimethylphenyl, 2 , 4 , 6-Trimethylphenyl oder 2,6-Dimetho- xyphenyl .R 1 is in particular phenyl, 2, 6-dichlorophenyl, 2, 4, 6-trichlorophenyl, 2, 6-dimethylphenyl, 2, 4, 6-trimethylphenyl or 2,6-dimethoxyphenyl.
R2 ist bevorzugt 2 , 4, 4-Trimethylpentyl , Benzyl, p-Chlorbenzyl,R 2 is preferably 2, 4, 4-trimethylpentyl, benzyl, p-chlorobenzyl,
2 , 4-Dichlorbenzyl, p-Methoxybenzyl , Methoxy, Ethoxy, n-Propyloxy,2, 4-dichlorobenzyl, p-methoxybenzyl, methoxy, ethoxy, n-propyloxy,
40 iso-Propyloxy, n-Butyloxy, iso-Butyloxy, sek. -Butyloxy, tert. -Butyloxy, 6-Hydroxy-l, 4-dioxohexyl, 9-Hydroxy-l , 4, 7-trioxononyl, 12-Hydroxy-l ,4,7, 10-tetraoxododecyl , 6-Methoxy-l , 4-dioxohexyl , 9-Methoxy-l, 4, 7-trioxononyl, 12-Methoxy-l, 4,7, 10-tetraoxododecyl, 6-Ethoxy-l, 4-dioxohexyl , 9-Ethoxy-l, 4, 7-trioxononyl ,40 iso-propyloxy, n-butyloxy, iso-butyloxy, sec. -Butyloxy, tert. -Butyloxy, 6-hydroxy-l, 4-dioxohexyl, 9-hydroxy-l, 4, 7-trioxononyl, 12-hydroxy-l, 4,7, 10-tetraoxododecyl, 6-methoxy-l, 4-dioxohexyl, 9 -Methoxy-l, 4, 7-trioxononyl, 12-methoxy-l, 4,7, 10-tetraoxododecyl, 6-ethoxy-l, 4-dioxohexyl, 9-ethoxy-l, 4, 7-trioxononyl,
45 12-Ethoxy-l , 4,7, 10-tetraoxododecyl , 8-Hydroxy-l , 5-dioxooctyl ,45 12-ethoxy-l, 4,7, 10-tetraoxododecyl, 8-hydroxy-l, 5-dioxooctyl,
12-Hydroxy-l, 5 , 9-trioxooctyl, 16-Hydroxy-l , 5,9, 13-tetraoxohexade- cyl, 10-Hydroxy-l, 6-dioxodecyl , 15-Hydroxy-l , 6, 11-trioxopentade- cyl, Vinyl, 1-Propenyl, Allyl, Methallyl, 1 , 1-Dirnethylallyl , 2-Butenyl, 2-Hexenyl, 2-Phenylviny1 , 2-Methoxyvinyl , 2-Ethoxyvi- nyl, 2-Chlorvinyl, Phenyl, Tolyl, Xylyl, α-Naphthyl, ß-Naphthyl, 4-Diphenylyl , 2-, 3- oder 4-Chlorphenyl , 2,4- oder 2,6-Dichlor- phenyl, 2 , 4, 6-Trichlorphenyl, 2-, 3- oder 4-Methylphenyl, 2,4- oder 2, 6-Dimethylphenyl , 2 , 4, 6-Trimethylphenyl , 2-, 3- oder 4-Ethylphenyl, 2,4- oder 2 , 6-Diethylphenyl , 2-, 3- oder 4-iso- Propylphenyl , 2-, 3- oder 4-tert . -Butylphenyl, 2-, 3- oder 4-Me- thoxyphenyl, 2,4- oder 2 , 6-Dimethoxyphenyl , 2-, 3- oder 4-Ethoxy- phenyl, Methylnaphthyl, Chlornaphthyl, Ethoxynaphthyl, 2,6-Dime- thylphenyl, 2 , 4 , 6-Trimethylphenyl , 2,4- oder 2 , 6-Dimethoxyphenyl, 2,4- oder 2 , 6-Dichlorphenyl , 2- oder 4-Nitrophenyl , 2,4- oder 2 , 6-Dinitrophenyl, 4-Dimethylaminophenyl , 4-Acetylphenyl oder R1-(C=Y)-.12-hydroxy-l, 5, 9-trioxooctyl, 16-hydroxy-l, 5.9, 13-tetraoxohexadecyl, 10-hydroxy-l, 6-dioxodecyl, 15-hydroxy-l, 6, 11-trioxopentade- cyl, vinyl, 1-propenyl, allyl, methallyl, 1, 1-dirnethylallyl, 2-butenyl, 2-hexenyl, 2-phenylviny1, 2-methoxyvinyl, 2-ethoxyvinyl, 2-chlorovinyl, phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-diphenylyl, 2-, 3- or 4-chlorophenyl, 2,4- or 2,6-dichlorophenyl, 2, 4, 6-trichlorophenyl, 2-, 3- or 4 -Methylphenyl, 2,4- or 2, 6-dimethylphenyl, 2, 4, 6-trimethylphenyl, 2-, 3- or 4-ethylphenyl, 2,4- or 2, 6-diethylphenyl, 2-, 3- or 4 -isopropylphenyl, 2-, 3- or 4-tert. -Butylphenyl, 2-, 3- or 4-methoxyphenyl, 2,4- or 2, 6-dimethoxyphenyl, 2-, 3- or 4-ethoxyphenyl, methylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dime- thylphenyl, 2, 4, 6-trimethylphenyl, 2,4- or 2, 6-dimethoxyphenyl, 2,4- or 2, 6-dichlorophenyl, 2- or 4-nitrophenyl, 2,4- or 2, 6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl or R 1 - (C = Y) -.
R2 ist besonders bevorzugt Benzyl, p-Chlorbenzyl, 2 , 4-Dichlorben- zyl, p-Methoxybenzyl, Methoxy, Ethoxy, n-Propyloxy, iso-Propyloxy, n-Butyloxy, iso-Butyloxy, sek. -Butyloxy, tert . -Butyloxy, 6-Hydroxy-l , 4-dioxohexyl , 9-Hydroxy-l , 4 , 7-trioxononyl , 12-Hy- droxy-1, 4, 7, 10-tetraoxododecyl, 6-Methoxy-l , 4-dioxohexyl, 9-Me- thoxy-1, 4, 7-trioxononyl, 12-Methoxy-l , 4,7, 10-tetraoxododecyl, 6-Ethoxy-l , 4-dioxohexyl , 9-Ethoxy-l , 4 , 7-trioxononyl , 12-Ethoxy-l, 4,7, 10-tetraoxododecyl , 8-Hydroxy-l, 5-dioxooctyl, 12-Hydroxy-l, 5, 9-trioxooctyl, 16-Hydroxy-l , 5,9, 13-tetraoxohexade- cyl, 10-Hydroxy-l, 6-dioxodecyl, 15-Hydroxy-l, 6, 11-trioxopentade- cyl, Vinyl, 2-Butenyl, 2-Phenylviny1 , Phenyl, Tolyl, Xylyl, α-Naphthyl, ß-Naphthyl, 4-Diphenylyl , 2-, 3- oder 4-Chlorphenyl , 2,4- oder 2 , 6-Dichlorphenyl, 2 , 4, 6-Trichlorphenyl , 2-, 3- oder 4-Methylphenyl, 2,4- oder 2 , 6-Dimethylphenyl , 2 , 4 , 6-Trimethylphe- nyl, 2-, 3- oder 4-Ethylphenyl, 2-, 3- oder 4-iso-Propylphenyl , 2-, 3- oder 4-tert . -Butylphenyl , 2-, 3- oder 4-Methoxyphenyl , 2,4- oder 2, 6-Dimethoxyphenyl, 2-, 3- oder 4-Ethoxyphenyl, Methylnaphthyl, Chlornaphthyl, Ethoxynaphthyl, 2- oder 4-Nitrophenyl, 2,4- oder 2 , 6-Dinitrophenyl, 4-Dimethylaminophenyl, 4-Ace- tylphenyl oder R1-(C=Y)-.R 2 is particularly preferably benzyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, methoxy, ethoxy, n-propyloxy, iso-propyloxy, n-butyloxy, iso-butyloxy, sec. -Butyloxy, tert. -Butyloxy, 6-hydroxy-l, 4-dioxohexyl, 9-hydroxy-l, 4, 7-trioxononyl, 12-hydroxy-1, 4, 7, 10-tetraoxododecyl, 6-methoxy-l, 4-dioxohexyl , 9-methoxy-1, 4, 7-trioxononyl, 12-methoxy-l, 4.7, 10-tetraoxododecyl, 6-ethoxy-l, 4-dioxohexyl, 9-ethoxy-l, 4, 7-trioxononyl , 12-ethoxy-l, 4,7, 10-tetraoxododecyl, 8-hydroxy-l, 5-dioxooctyl, 12-hydroxy-l, 5, 9-trioxooctyl, 16-hydroxy-l, 5.9, 13-tetraoxohexad - Cyl, 10-hydroxy-l, 6-dioxodecyl, 15-hydroxy-l, 6, 11-trioxopentadecyl, vinyl, 2-butenyl, 2-phenylviny1, phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl , 4-diphenylyl, 2-, 3- or 4-chlorophenyl, 2,4- or 2,6-dichlorophenyl, 2, 4, 6-trichlorophenyl, 2-, 3- or 4-methylphenyl, 2,4- or 2 , 6-dimethylphenyl, 2, 4, 6-trimethylphenyl, 2-, 3- or 4-ethylphenyl, 2-, 3- or 4-iso-propylphenyl, 2-, 3- or 4-tert. -Butylphenyl, 2-, 3- or 4-methoxyphenyl, 2,4- or 2, 6-dimethoxyphenyl, 2-, 3- or 4-ethoxyphenyl, methylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2- or 4-nitrophenyl, 2,4 - or 2, 6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl or R 1 - (C = Y) -.
R2 ist ganz besonders bevorzugt Methoxy, Ethoxy, n-Propoxy, iso- Propoxy, n-Butyloxy, sek-Butyloxy, iso-Butyloxy, tert-Butyloxy, 6-Hydroxy-l , 4-dioxohexyl , 9-Hydroxy-l , 4 , 7-trioxononyl , 12-Hy- droxy-1, 4, 7, 10-tetraoxododecyl, 8-Hydroxy-l, 5-dioxooctyl, 12-Hy- droxy-1 , 5 , 9-trioxooctyl , 16-Hydroxy-l ,5,9, 13-tetraoxohexadecyl , 10-Hydroxy-l , 6-dioxodecyl , 15-Hydroxy-l , 6 , 11-trioxopentadecyl , Phenyl, Xylyl, α-Naphthyl, ß-Naphthyl, 4-Diphenylyl, 2-, 3- oder 4-Chlorphenyl, 2 , 4-Dichlorphenyl , 2-, 3- oder 4-Methylphenyl , 2,4-Dimethylphenyl, 2-, 3- oder 4-Ethylphenyl, 2-, 3- oder 4-Me- thoxyphenyl, 2 , 4-Dimethoxyphenyl , 2-, 3- oder 4-Ethoxyphenyl , Me- thylnaphthyl , Chlornaphthyl, Ethoxynaphthyl, 2- oder 4-Nitrophenyl oder R1-(C=Y)-.R 2 is very particularly preferably methoxy, ethoxy, n-propoxy, iso-propoxy, n-butyloxy, sec-butyloxy, iso-butyloxy, tert-butyloxy, 6-hydroxy-l, 4-dioxohexyl, 9-hydroxy-l, 4, 7-trioxononyl, 12-hydroxy-1, 4, 7, 10-tetraoxododecyl, 8-hydroxy-l, 5-dioxooctyl, 12-hydroxy-1, 5, 9-trioxooctyl, 16-hydroxy- l, 5,9,13-tetraoxohexadecyl, 10-hydroxy-l, 6-dioxodecyl, 15-hydroxy-l, 6, 11-trioxopentadecyl, phenyl, xylyl, α-naphthyl, ß-naphthyl, 4-diphenylyl, 2- , 3- or 4-chlorophenyl, 2, 4-dichlorophenyl, 2-, 3- or 4-methylphenyl, 2,4-dimethylphenyl, 2-, 3- or 4-ethylphenyl, 2-, 3- or 4-Me- thoxyphenyl, 2, 4-dimethoxyphenyl, 2-, 3- or 4-ethoxyphenyl, Me- thylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2- or 4-nitrophenyl or R 1 - (C = Y) -.
R2 ist insbesondere Methoxy, Ethoxy, n-Propoxy, iso-Propoxy, n-Bu- tyloxy, sek-Butyloxy, iso-Butyloxy, tert-Butyloxy, Phenyl, 4-Di- phenylyl, 2-, 3- oder 4-Chlorphenyl , 2-, 3- oder 4-Methylphenyl, 2-, 3- oder 4-Methoxyphenyl oder 2-, 3- oder 4-Ethoxyphenyl . R2 ist speziell Phenyl, Methoxy oder Ethoxy.R 2 is in particular methoxy, ethoxy, n-propoxy, iso-propoxy, n-butyloxy, sec-butyloxy, iso-butyloxy, tert-butyloxy, phenyl, 4-diphenylyl, 2-, 3- or 4- Chlorophenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-methoxyphenyl or 2-, 3- or 4-ethoxyphenyl. R 2 is specifically phenyl, methoxy or ethoxy.
Y ist bevorzugt 0, S oder NR3.Y is preferably 0, S or NR 3 .
Y ist besonders bevorzugt 0 oder S und ganz besonders bevorzugt 0.Y is particularly preferably 0 or S and very particularly preferably 0.
Z ist bevorzugt 0, S, NR3 oder ein freies Elektronenpaar, besonders bevorzugt 0, S oder ein freies Elektronenpaar, ganz besonders bevorzugt 0 oder S und insbesondere 0.Z is preferably 0, S, NR 3 or a free electron pair, particularly preferably 0, S or a free electron pair, very particularly preferably 0 or S and in particular 0.
R3 ist bevorzugt Wasserstoff, Methyl, tert. -Butyl, Phenyl oder S03H, besonders bevorzugt Wasserstoff, tert. -Butyl, Phenyl oder S03H und ganz besonders bevorzugt Wasserstoff, tert. -Butyl oder Phenyl .R 3 is preferably hydrogen, methyl, tert. -Butyl, phenyl or S0 3 H, particularly preferably hydrogen, tert. -Butyl, phenyl or S0 3 H and very particularly preferably hydrogen, tert. -Butyl or phenyl.
R4 ist bevorzugt Wasserstoff, Methyl, Phenyl, 2 , 4-Dinitrophenyl, Carbamoyl, Phenylsulfonyl oder 4-Methylphenylsulfonyl , besonders bevorzugt Wasserstoff, Phenyl, 2, 4-Dinitrophenyl oder Phenylsul- fonyl, ganz besonders bevorzugt Wasserstoff, 2 , 4-Dinitrophenyl oder Phenylsulfonyl und insbesondere Wasserstoff oder 2,4-Dini- trophenyl .R 4 is preferably hydrogen, methyl, phenyl, 2, 4-dinitrophenyl, carbamoyl, phenylsulfonyl or 4-methylphenylsulfonyl, particularly preferably hydrogen, phenyl, 2, 4-dinitrophenyl or phenylsulfonyl, very particularly preferably hydrogen, 2, 4-dinitrophenyl or phenylsulfonyl and especially hydrogen or 2,4-dinitrophphenyl.
R5 ist bevorzugt Wasserstoff, Methoxy, Methyl oder Ethyl.R 5 is preferably hydrogen, methoxy, methyl or ethyl.
R5 ist besonders bevorzugt Wasserstoff oder Methyl.R 5 is particularly preferably hydrogen or methyl.
R5 ist ganz besonders bevorzugt Wasserstoff.R 5 is very particularly preferably hydrogen.
R6 ist bevorzugt Wasserstoff, Methoxy, Phenyl, Methyl oder Ethyl, besonders bevorzugt Wasserstoff, Phenyl oder Methyl und ganz besonders bevorzugt Wasserstoff.R 6 is preferably hydrogen, methoxy, phenyl, methyl or ethyl, particularly preferably hydrogen, phenyl or methyl and very particularly preferably hydrogen.
R7 ist bevorzugt Wasserstoff, Methoxy, Phenyl, Methyl oder Ethyl, besonders bevorzugt Wasserstoff, Phenyl oder Methyl und ganz besonders bevorzugt Wasserstoff. R8 ist bevorzugt Wasserstoff, Methyl, Ethyl, n-Butyl oder Phenyl, besonders bevorzugt Wasserstoff oder Methyl und ganz besonders bevorzugt Wasserstoff.R 7 is preferably hydrogen, methoxy, phenyl, methyl or ethyl, particularly preferably hydrogen, phenyl or methyl and very particularly preferably hydrogen. R 8 is preferably hydrogen, methyl, ethyl, n-butyl or phenyl, particularly preferably hydrogen or methyl and very particularly preferably hydrogen.
RG ist bevorzugt Vinyl, l-Propen-2-yl, Acryl (HC=CH (CO) -) , Acryloxi (H2C=CH (CO) 0-) , Methacryloxy, Acrylamido, Methacrylamido, Hy- droxy (-0H) , Mercapto (-SH) , Amino (-NH2) , Carboxyl (-C00H) , oder Carboxylat (-C00") , besonders bevorzugt Vinyl, Acryl, Acryloxi, Methacryloxy, Acrylamido, Hydroxy (-OH) , Amino (-NH2) oder Carbo- xyl (-COOH) , ganz besonders bevorzugt Vinyl, Acryloxi, Methacryloxy, Hydroxy (-OH) oder Amino (-NH2) und insbesondere Acryloxy.RG is preferably vinyl, l-propen-2-yl, acrylic (HC = CH (CO) -), acryloxy (H 2 C = CH (CO) 0-), methacryloxy, acrylamido, methacrylamido, hydroxy (-0H ), Mercapto (-SH), amino (-NH 2 ), carboxyl (-C00H), or carboxylate (-C00 "), particularly preferably vinyl, acrylic, acryloxy, methacryloxy, acrylamido, hydroxy (-OH), amino (- NH 2 ) or carboxyl (-COOH), very particularly preferably vinyl, acryloxy, methacryloxy, hydroxy (-OH) or amino (-NH 2 ) and in particular acryloxy.
n ist bevorzugt von 1 bis 10, besonders bevorzugt von 1 bis 5 , ganz besonders bevorzugt von 1 bis 3 und insbesondere 1.n is preferably from 1 to 10, particularly preferably from 1 to 5, very particularly preferably from 1 to 3 and in particular 1.
Insbesondere sind von den Acyl- und Bisacylphosphinderivaten, die durch die Formel (I) beschrieben sind, die folgenden Individuen 1-1 bis 1-211 bevorzugt, in denen die Reste in Formel (I) die folgenden Bedeutungen haben:In particular, of the acyl and bisacylphosphine derivatives described by formula (I), the following individuals 1-1 to 1-211 are preferred, in which the radicals in formula (I) have the following meanings:
Figure imgf000016_0001
Figure imgf000016_0001
Figure imgf000017_0001
Figure imgf000017_0001
Figure imgf000019_0001
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000025_0001
Figure imgf000026_0001
DMP : 2 , 6-Dimethyl-l-phenylDMP: 2,6-dimethyl-1-phenyl
DMOP : 2 , 6-Dimethoxy-l-phenylDMOP: 2,6-dimethoxy-l-phenyl
DCP : 2 , 6-Dichlor-l-phenylDCP: 2,6-dichloro-1-phenyl
TMB: 2, 4, 6-TrimethylbenzoylTMB: 2, 4, 6-trimethylbenzoyl
Ph: PhenylPh: phenyl
EtO : EthoxyEtO: ethoxy
Wie oben ausgeführt, sind auch solche Individuen aus der Tabelle bevorzugt, bei denen R2 4-Methylphenyl , 4-Methoxyphenyl , 4-Chlor- phenyl, Methoxy, n-Propoxy, iso-Propoxy, n-Butoxy, seic-Butoxy, iso-Butoxy oder tert-Butoxy sind. Wie oben ausgeführt, sind auch solche Individuen aus der Tabelle bevorzugt, bei denen R1 ortho-substituiert sind, beispielsweise 2-Methylphenyl, 2-Methoxyphenyl oder 2-Chlorphenyl .As stated above, those individuals from the table are preferred in which R 2 is 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl, methoxy, n-propoxy, iso-propoxy, n-butoxy, seic-butoxy, iso -Butoxy or tert-butoxy. As stated above, preference is also given to those individuals from the table in whom R 1 are ortho-substituted, for example 2-methylphenyl, 2-methoxyphenyl or 2-chlorophenyl.
Weiterhin ist ein Verfahren zur Herstellung von Acyl- und Bisa- cylphosphinderivaten der Formel (I) Gegenstand der vorliegenden Erfindung, in dem man einen Stoff H-X-RGn oder θX-RGn mit einer Verbindung der Formel (III) ,The present invention furthermore relates to a process for the preparation of acyl and bis-acylphosphine derivatives of the formula (I), in which a substance HX-RG n or θ X-RG n with a compound of the formula (III),
Figure imgf000027_0001
Figure imgf000027_0001
worin X, RG und n die obigen Bedeutungen haben,in which X, RG and n have the meanings given above,
FG eine Abgangsgruppe der Struktur -F, -Cl, -I, -CN, -OCN, -SCN, -N+R15R16R17, -0(C0)R14, -0(CO)OR14, -0(C0)NR14, -N(C0)NR14, -0(S0)C1, -0(S02)C1, -0(S02)R14, -0(S02)OR14, -0(C0)C1, -0(NO)OR14, -SR14, -Br, - (NR12) -NR13R18 oderFG a leaving group of the structure -F, -Cl, -I, -CN, -OCN, -SCN, -N + R 15 R 16 R 17 , -0 (C0) R 14 , -0 (CO) OR 14 , - 0 (C0) NR 14 , -N (C0) NR 14 , -0 (S0) C1, -0 (S0 2 ) C1, -0 (S0 2 ) R 14 , -0 (S0 2 ) OR 14 , -0 (C0) C1, -0 (NO) OR 14 , -SR 14 , -Br, - (NR 12 ) -NR 13 R 18 or
-(NR12)-OR18,- (NR 12 ) -OR 18 ,
R12 Wasserstoff, Ci bis C4-Alkyl, S03H, Phenyl oder Acetyl,R 12 is hydrogen, Ci to C 4 alkyl, S0 3 H, phenyl or acetyl,
R13 Wasserstoff, Ci bis C4-Alkyl, COOR3 oder gegebenenfalls durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/ oder Heterocyclen substituiertes Cβ - Cj_ -Aryl oder Aryl- sulfonyl,R 13 is hydrogen, Ci to C 4 alkyl, COOR 3 or Cβ-Cj-aryl or arylsulfonyl which is optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles,
R14 gegebenenfalls durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiertes Ci - Ciβ-Alkyl, gegebenenfalls durch ein oder mehrere Sauerstoff-, Stickstoff- und/oder Schwefelatome unterbrochenes C2 - Cis-Alkyl, gegebenenfalls durch Aryl, Alkyl, Ary- loxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiertes Ci - Cis-Alkoxy, gegebenenfalls durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiertes C - Ciβ-Alkenyl, gegebenenfalls durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder He- terocyclen substituiertes Cς, - Cι2-Aryl, gegebenenfalls durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/ oder Heterocyclen substituiertes C5 - Cι2-Cycloalkyl oder einen fünf- bis sechsgliedrigen, Sauerstoff-, Stickstoff- und/oder Schwefelatome aufweisenden Heterocyclus, R15, R16 gegebenenfalls durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiertes Ci - Ciβ-Alkyl, gegebenenfalls durch ein oder mehrere Sauerstoff-, Stickstoff- und/oder Schwefelatome unterbrochenes C2 - C18-Alkyl, gegebenenfalls durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiertes C2 - Cis-Alkenyl, gegebenenfalls durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiertes C6 - Cι2-Aryl, gegebenenfalls durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiertes C5 - Cι2-Cycloalkyl oder einen fünf- bis sechsgliedrigen, Sauerstoff-, Stickstoff- und/oder Schwefelatome aufweisenden Heterocyclus,R 14 optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles Ci - Ciβ alkyl, optionally interrupted by one or more oxygen, nitrogen and / or sulfur atoms C 2 - cis alkyl, optionally by aryl, Alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles substituted Ci - Cis-alkoxy, optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles C - Ciβ-alkenyl, optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles Cς, - Cι 2 -aryl, optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles substituted C 5 - Cι 2 cycloalkyl or a five- to six-membered, oxygen- Heterocycle having nitrogen and / or sulfur atoms, R 15 , R 16 optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles Ci - Ciβ-alkyl, optionally interrupted by one or more oxygen, nitrogen and / or sulfur atoms C 2 - C 18 alkyl, optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles C 2 - cis alkenyl, optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles C 6 -C 2 aryl, optionally substituted by aryl , Alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles substituted C 5 -C 2 cycloalkyl or a five- to six-membered heterocycle having oxygen, nitrogen and / or sulfur atoms,
R17 gegebenenfalls durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiertes Ci - Cis-Alkyl oder gegebenenfalls durch ein oder mehrere Sauerstoff-, Stickstoff- und/oder Schwefelatome unterbrochenes C2 - Ciβ-Alkyl sowieR 17 optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles Ci - Cis-alkyl or optionally interrupted by one or more oxygen, nitrogen and / or sulfur atoms C 2 - Ciβ-alkyl and
Rl8 Wasserstoff oder Ci bis C -Alkyl,Rl8 is hydrogen or Ci to C alkyl,
bedeuten,mean,
umsetzt.implements.
Weiterhin sind dimere Acyl- und Bisacylphosphinoxide der Formel (II) Gegenstand der vorliegenden Erfindung,The present invention furthermore relates to dimeric acyl and bisacylphosphine oxides of the formula (II),
Figure imgf000028_0001
Figure imgf000028_0001
worin R1, R2 , Y und Z die oben genannten Bedeutungen haben und R1', R2', Y' und Z' die gleichen Bedeutungen haben wie R1, R2, Y und Z, jedoch von diesen verschieden sein können. In Het1-X-Het2 hat X die obige Bedeutung und Het1 und Het2 bedeuten unabhängig voneinander 0, S oder NR9.wherein R 1 , R 2 , Y and Z have the meanings given above and R 1 ', R 2 ', Y 'and Z' have the same meanings as R 1 , R 2 , Y and Z, but can be different from these , In Het 1 -X-Het 2 , X has the above meaning and Het 1 and Het 2 independently of one another mean 0, S or NR 9 .
Weiterhin wird ein Verfahren zur Herstellung von Verbindungen des Typs (II) offenbart, in dem man Verbindungen der Formel (III) mit Verbindungen H-Heti-X-He^-H, ©Het1-X-Het -H, H-Het1-X-Het2© oder θHet1-X-Het2θ umgesetzt werden. Verbindungen der Formel (III) sind beispielsweise in der deutschen Anmeldung mit dem Titel "Acyl- und Bisacylphosphinderivate' und dem Aktenzeichen 10206117.3 mit dem Anmeldetag 13. Feb. 2002 beschrieben.Furthermore, a process for the preparation of compounds of type (II) is disclosed in which compounds of the formula (III) with compounds H-Het i -X-He ^ -H, © Het 1 -X-Het -H, H- Het 1 -X-Het 2 © or θ Het 1 -X-Het 2θ . Compounds of the formula (III) are described, for example, in the German application entitled "Acyl and bisacylphosphine derivatives" and the file number 10206117.3 with the filing date Feb. 13, 2002.
Die Phosphinderivate der Formel (III) können durch ein Verfahren hergestellt werden, in dem man einen Stoff der FormelThe phosphine derivatives of the formula (III) can be prepared by a process in which a substance of the formula
ZZ
Figure imgf000029_0001
Figure imgf000029_0001
worin R1, R2 , Y und Z die oben genannte Bedeutung haben undwherein R 1 , R 2 , Y and Z have the meaning given above and
X' Wasserstoff oder ein Kation ist,X 'is hydrogen or a cation,
mit mindestens einem Mittel umsetzt, das die Gruppe -OX' in eine Gruppe -FG wie in Formel (III) überführt.with at least one agent which converts the group -OX 'into a group -FG as in formula (III).
Kationen können dabei beispielsweise solche sein, wie in der EP-A 62 839 aufgeführt, also Äquivalente eines Kations der 1. bis 3. Hauptgruppe des Periodensystems mit einem Molgewicht unter 138 oder Ammoniumionen, abgeleitet von quartären Ammoniumionen oder Triethylendiammoniumionen .Cations can be, for example, those as listed in EP-A 62 839, that is, equivalents of a cation of the 1st to 3rd main group of the periodic table with a molecular weight below 138 or ammonium ions derived from quaternary ammonium ions or triethylene diammonium ions.
Mittel, die die Gruppe -OX' in die Gruppe -FG überführen sind dem Fachmann an sich bekannt. Beispielhaft seien genannt Phosgen (C0C12) , Thionylchlorid (S0C12) , Sulfurylchlorid (S02C12) , Phosp- hortrichlorid (PCl3) , Phosphoroxidtrichlorid (P0C13) , Phosphorpen- tachlorid (PC15) , Oxalylchlorid ((C0C1)2), Chlorwasserstoff (HC1) , Chlorgas (Cl2) , N-Chlorverbindungen, wie z.B. N-Chlorsuccinimid, Alkalifluoride, Cobalt (III) -fluorid, Halogenfluoride, Antimon- fluoride, Molybdänfluorid, Fluorwasserstoff , Fluorwasserstoff/ Pyridin-Gemische , Xenonfluoride und andere Edelgas-Verbindungen, gasförmiges Fluor, Schwefeltetrafluorid, Iod, Iodmonochlorid, Phosphortriiodid, Säureiodide, N-Iodsuccinimid, N-Iodacetamid, Chlorcyan (ClCN) , Cyanurchlorid (2 , 4 , 6-Trichlor-l , 3 , 5-triazin, C3C13N3) , Säurechloride (R5(C0)C1), -ester oder -anhydride (R5(C0)20), Kohlensäurechloride (R50 (CO) CI) ) , Carbonate ( (R50)2 (CO) ) , Sulfonsäurechloride (R5S02C1) oder Sulfonsäureanhy- dride ( (R5S02)20) .Agents which convert the group -OX 'into the group -FG are known per se to the person skilled in the art. Examples include phosgene (C0C1 2 ), thionyl chloride (S0C1 2 ), sulfuryl chloride (S0 2 C1 2 ), phosphorus trichloride (PCl 3 ), phosphorus oxychloride (P0C1 3 ), phosphorus pentachloride (PC1 5 ), oxalyl chloride ((C0C1) 2 ), hydrogen chloride (HC1), chlorine gas (Cl 2 ), N-chlorine compounds such as N-chlorosuccinimide, alkali fluoride, cobalt (III) fluoride, halogen fluoride, antimony fluoride, molybdenum fluoride, hydrogen fluoride, hydrogen fluoride / pyridine mixtures, xenon fluoride and other noble gas compounds, gaseous fluorine, sulfur tetrafluoride, iodine, iodine monochloride, phosphorus triiodide, acid iodides, N-iodosuccinimide, N-iodoacetamide, cyanogen chloride (ClCN), cyanuric chloride (2, 4, 6-trichloro-l, 3, 5-triazine, C 3 C1 3 N 3), acyl chlorides (R 5 (C0) C1), esters or anhydrides (R 5 (C0) 2 0), carbonic acid chlorides (R 5 0 (CO) CI)), carbonates ((R 5 0) 2 (CO)), sulfonic acid chlorides (R 5 S0 2 C1) or sulfonic acid anhydrides ((R 5 S0 2 ) 2 0).
Beispiele für Verbindungen der Formel H-Hetx-X-Het2-H, beziehungsweise deren Anionen, sind Polyethylenglykole mit einer Molmasse zwischen 106 und 898, besonders Ethylenglykol , Diethylenglykol, Triethylenglykol, Tetraethylenglykol , 1 , 2-Propylenglykol, Poly-1, 2-Propylenglykol mit einer Molmasse zwischen 134 und 1178, 1, 3-Propylenglykol , Poly-1, 3-Propylenglykol mit einer Molmasse zwischen 134 und 1178, 1, 4-Butandiol, Poly-THF mit einer Molmasse zwischen 162 und 1458, 1 , 6-Hexandiol , 1 , 8-0ctandiol , 1,10-Decan- diol, 1, 12-Dodecandiol, 2-Ethylhexan-l , 3-diol, 2 , 4-Diethyloc- tan-1, 3-diol, Trimethylolpropan, Trimethylolethan, Neopentylgly- kol, Pentaerythrit, 2-Methyl-l, 3-Propandiol, Glycerin, Ditrime- thylolpropan, Dipentaerythrit, Bisphenol A, Bisphenol F, Bisphe- nol B, Bisphenol S, 2, 2-Bis (4-hydroxycyclohexyl) propan, 1,1-, 1,2-, 1,3- und 1, 4-Cyclohexandimethanol, 1,2-, 1,3- oder 1,4-Cy- clohexandiol , 2-Thioethanol, 2-Aminoethanol , 2- oder 3-Aminopro- panol, 4-Aminobutanol, 6-Aminohexanol, Aminoethylethanolamin, Mo- noethanolamin, Diethanolamin, Triethanolamin, O-Hydroxyethyltrie- thanolamin, Monopropanolamin, Dipropanolamin, Tripropanolamin, Ethylendiamin, 1, 6-Hexandiamin, Diethylentriamin, Triethylente- tramin, Piperazin, 6-Hydroxycapronsäure, 6-Aminocapronsäure, Ami- noessigsäure, Hydroxyessigsäure, 2-Aminopropionsäure, Dimethylol- propionsäure, Dirnethylolbuttersäure, Fumarsäure, Maleinsäure, Bernsteinsäure, Adidpinsäure, Maleinsäureanhydrid, 1,2-, 1,3- oder 1, 4-Aminophenol, 1,2-, 1,3- oder 1 , 4-Bishydroxymethylbenzol , 2-, 3- oder 4-Hydroxybenzoesäure oder 2-, 3- oder 4-Aminobenzoe- säure .Examples of compounds of the formula H-Het x -X-Het 2 -H, or their anions, are polyethylene glycols with a molecular weight between 106 and 898, especially ethylene glycol, diethylene glycol, Triethylene glycol, tetraethylene glycol, 1, 2-propylene glycol, poly-1, 2-propylene glycol with a molecular weight between 134 and 1178, 1, 3-propylene glycol, poly-1, 3-propylene glycol with a molecular weight between 134 and 1178, 1, 4- Butanediol, poly-THF with a molecular weight between 162 and 1458, 1, 6-hexanediol, 1, 8-0ctanediol, 1,10-decanediol, 1, 12-dodecanediol, 2-ethylhexan-l, 3-diol, 2 , 4-Diethyloc- tan-1, 3-diol, trimethylolpropane, trimethylolethane, neopentyl glycol, pentaerythritol, 2-methyl-l, 3-propanediol, glycerol, ditrimethyl propane, dipentaerythritol, bisphenol A, bisphenol F, bisphenol B, bisphenol S, 2,2-bis (4-hydroxycyclohexyl) propane, 1,1-, 1,2-, 1,3- and 1,4-cyclohexanedimethanol, 1,2-, 1,3- or 1, 4-cyclohexanediol, 2-thioethanol, 2-aminoethanol, 2- or 3-aminopropanol, 4-aminobutanol, 6-aminohexanol, aminoethylethanolamine, monoethanolamine, diethanolamine, triethanolamine, O-hydroxyethyltriethanolamine, monopropanolamine, dipropanolamine , Tripropanolamine, ethylenediami n, 1, 6-hexanediamine, diethylenetriamine, triethylenetetramine, piperazine, 6-hydroxycaproic acid, 6-aminocaproic acid, aminoacetic acid, hydroxyacetic acid, 2-aminopropionic acid, dimethylol propionic acid, dirnethylolbutyric acid, fumaric acid, maleic acid, succinic acid, maleic acid, maleic acid, maleic acid, 1,2-, 1,3- or 1,4-aminophenol, 1,2-, 1,3- or 1,4-bishydroxymethylbenzene, 2-, 3- or 4-hydroxybenzoic acid or 2-, 3- or 4- Aminobenzoic acid.
Denkbar sind auch Polether- und Polyesterole mit einer mittleren OH-Funktionalität von 2 bis 10, die bevorzugt ein Molgewicht von 200 bis 2000 aufweisen.Polether and polyesterols with an average OH functionality of 2 to 10, which preferably have a molecular weight of 200 to 2000, are also conceivable.
Insbesondere sind von den dimeren Acyl- und Bisacylphosphinderi- vaten, die durch die Formel (II) beschrieben sind, die folgenden Individuen II-l bis 11-78 bevorzugt, in denen die Reste in Formel (II) die folgenden Bedeutungen haben:In particular, of the dimeric acyl and bisacylphosphine derivatives described by the formula (II), the following individuals II-1 to 11-78 are preferred, in which the radicals in formula (II) have the following meanings:
Figure imgf000030_0001
Figure imgf000031_0001
oε
Figure imgf000030_0001
Figure imgf000031_0001
oε
0.OΪO/εθd3/X3d S8.890/C0 OΛV
Figure imgf000032_0001
Figure imgf000033_0001
0.OΪO / εθd3 / X3d S8.890 / C0 OΛV
Figure imgf000032_0001
Figure imgf000033_0001
TMP : 2,4, 6-Trimethyl-1-phenylTMP: 2,4,6-trimethyl-1-phenyl
DMP : 2 , 6-Dimethyl-l-phenylDMP: 2,6-dimethyl-1-phenyl
DMOP : 2 , 6-Dirnethoxy-1-phenylDMOP: 2,6-dirthethoxy-1-phenyl
DCP : 2 , 6-Dichlor-l-phenylDCP: 2,6-dichloro-1-phenyl
TMB: 2 , 4 , 6-TrimethylbenzoylTMB: 2, 4, 6-trimethylbenzoyl
Ph: PhenylPh: phenyl
EtO : EthoxyEtO: ethoxy
Wie oben ausgeführt, sind auch solche Individuen aus der Tabelle bevorzugt, bei denen R2 4-Methylphenyl , 4-Methoxyphenyl , 4-Chlor- phenyl, Methoxy, n-Propoxy, iso-Propoxy, n-Butoxy, seJc-Butoxy, iso-Butoxy oder tert-Butoxy sind. Wie oben ausgeführt, sind auch solche Individuen aus der Tabelle bevorzugt, bei denen R1 ortho-substituiert sind, beispielsweise 2-Methylphenyl, 2 , 6-Dimethyl-l-phenyl, 2-Methoxyphenyl, 2,6-Dime- thoxy-1-phenyl, 2 , 6-Dichlor-l-phenyl oder 2-Chlorphenyl .As stated above, preference is also given to those individuals from the table in whom R 2 is 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl, methoxy, n-propoxy, iso-propoxy, n-butoxy, seJc-butoxy, iso -Butoxy or tert-butoxy. As stated above, preference is also given to those individuals from the table in whom R 1 are ortho-substituted, for example 2-methylphenyl, 2, 6-dimethyl-1-phenyl, 2-methoxyphenyl, 2,6-dimethyl-1 -phenyl, 2, 6-dichloro-l-phenyl or 2-chlorophenyl.
Ein weiteres Verfahren zur Herstellung von Acyl- und Bisacyl- phosphinderivaten des Typs (II) besteht darin, Verbindungen der Formel (IV) ,Another process for the preparation of acyl and bisacylphosphine derivatives of type (II) consists of compounds of the formula (IV),
Figure imgf000034_0001
worin R1 ' , R2 ' , X, Y' , Z', Het1 und Het2 wie oben definiert sind,
Figure imgf000034_0001
wherein R 1 ', R 2 ', X, Y ', Z', Het 1 and Het 2 are as defined above,
mit Verbindungen der Formel (III) umzusetzen.react with compounds of formula (III).
Insbesondere sind von den Acyl- und Bisacylphosphinderivaten, die durch die Formel (IV) beschrieben sind, die folgenden Individuen IV-1 bis IV-78 bevorzugt, in denen die Reste in Formel (IV) die folgenden Bedeutungen haben:In particular, of the acyl and bisacylphosphine derivatives described by the formula (IV), the following individuals IV-1 to IV-78 are preferred, in which the radicals in formula (IV) have the following meanings:
Figure imgf000034_0002
Figure imgf000035_0001
Figure imgf000034_0002
Figure imgf000035_0001
Figure imgf000036_0001
DMP : 2 , 6-Dimethyl-l-phenyl
Figure imgf000036_0001
DMP: 2,6-dimethyl-1-phenyl
DMOP: 2, 6-Dirnethoxy-1-phenylDMOP: 2,6-dirthethoxy-1-phenyl
DCP: 2, 6-Dichlor-l-phenylDCP: 2,6-dichloro-1-phenyl
TMB : 2,4, 6-TrimethylbenzoylTMB: 2,4,6-trimethylbenzoyl
Ph: PhenylPh: phenyl
EtO : EthoxyEtO: ethoxy
Wie oben ausgeführt, sind auch solche Individuen aus der Tabelle bevorzugt, bei denen R2 4-Methylphenyl , 4-Methoxyphenyl, 4-Chlor- phenyl, Methoxy, n-Propoxy, iso-Propoxy, n-Butoxy, seic-Butoxy, iso-Butoxy oder tert-Butoxy sind.As stated above, those individuals from the table are preferred in which R 2 is 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl, methoxy, n-propoxy, iso-propoxy, n-butoxy, seic-butoxy, iso -Butoxy or tert-butoxy.
Wie oben ausgeführt, sind auch solche Individuen aus der Tabelle bevorzugt, bei denen R1 ortho-substituiert sind, beispielsweise 2-Methylphenyl, 2 , 6-Dirnethyl-1-phenyl , 2-Methoxyphenyl, 2,6-Dime- thoxy-1-phenyl , 2 , 6-Dichlor-l-phenyl oder 2-Chlorphenyl .As stated above, those individuals in the table in which R 1 are ortho-substituted, for example 2-methylphenyl, 2, 6-dimethyl-1-phenyl, 2-methoxyphenyl, 2,6-dimethoxy-1, are also preferred -phenyl, 2, 6-dichloro-l-phenyl or 2-chlorophenyl.
Die Durchführung der Umsetzung von (III) mit H-Het1-X-Het2-H beziehungsweise den entsprechenden Anionen oder der Umsetzung von (III) mit (IV) erfolgt beispielsweise folgendermaßen:The reaction of (III) with H-Het 1 -X-Het 2 -H or the corresponding anions or the reaction of (III) with (IV) is carried out, for example, as follows:
Zur Umsetzung mit (III) wird meist in Gegenwart von 0,9 bis 1,5 Moläquivalenten eines Säurefängers, wie Pyridin oder ein tertiäres Amin, wie z.B. Triethylamin, Tributylamin, Benzyldimethyla- min, Dimethyla inopyridin etc., bei Temperaturen zwischen 0 °C und 100 °C, bevorzugt zwischen 10 °C und 80 °C, das umzusetzende Substrat vorgelegt, gegebenenfalls gelöst in einem geeigneten Lösungsmittel, wie z.B. Benzol, Toluol, Xylol, Tetrahydrofuran, Hexan, Heptan, Pentan oder Petrolether, und dann (III) in einem Zeitraum von wenigen Minuten bis mehreren Stunden, bevorzugt 10 bis 300 Minuten, besonders bevorzugt 30 bis 180 Minuten unter kräftiger Durchmischung zugegeben. (III) kann ebenfalls in einem geeigneten Lösungsmittel gelöst eingesetzt werden, z.B. die genannten Lösungsmittel. Gegebenenfalls kann nachgerührt werden, beispielsweise 30 bis 600 Minuten, bevorzugt 60 bis 300 Minuten, wobei die Reaktionstemperatur stufenlangsam angehoben werden kann.The reaction with (III) is usually carried out in the presence of 0.9 to 1.5 molar equivalents of an acid scavenger, such as pyridine or a tertiary amine, e.g. Triethylamine, tributylamine, benzyldimethylaamine, dimethyla inopyridine etc., at temperatures between 0 ° C and 100 ° C, preferably between 10 ° C and 80 ° C, the substrate to be reacted, optionally dissolved in a suitable solvent, e.g. Benzene, toluene, xylene, tetrahydrofuran, hexane, heptane, pentane or petroleum ether, and then (III) in a period of a few minutes to several hours, preferably 10 to 300 minutes, particularly preferably 30 to 180 minutes with vigorous mixing. (III) can also be used dissolved in a suitable solvent, e.g. the solvents mentioned. If necessary, stirring can be continued, for example 30 to 600 minutes, preferably 60 to 300 minutes, it being possible for the reaction temperature to be raised gradually.
Das entstandene Reaktionsprodukt kann in roher oder aufgearbeite- ter Form weiterverarbeitet werden. Falls eine Weiterverwendung in reiner Form gewünscht wird, so kann das Produkt beispielsweise über Kristallisation und fest/ flüssig-Trennung oder über Destillation oder Rektifikation bei vermindertem Druck aufgereinigt werden.The resulting reaction product can be further processed in raw or processed form. If further use in pure form is desired, the product can be purified, for example, by crystallization and solid / liquid separation or by distillation or rectification under reduced pressure.
Die Ausbeuten liegen in der Regel über 75 %, meist über 80 % und häufig über 90 %.The yields are usually over 75%, mostly over 80% and often over 90%.
Die beschriebenen Mono- und Diacyl- oder dimeren Phosphinderivate sind verwendbar als Photoinitiatoren in photopolymerisierbaren Massen, z.B. Überzugsmittel, Lacke, Druckfarben, Aufzeichnungsma- terialien, wäßrige Lösungen, Dispersionen und Emulsionen.The mono- and diacyl or dimeric phosphine derivatives described can be used as photoinitiators in photopolymerizable compositions, e.g. Coating agents, lacquers, printing inks, recording materials, aqueous solutions, dispersions and emulsions.
Allgemein erfolgt Synthese von Acylphosphinoxiden (Z = 0) entspe- chend der Literatur (siehe z.B. EP-A 7508 und EP-A 62839) durch Umsetzung von Alkoxyphosphinen und Säurechloriden übertragen auf das vorliegende System gemäßIn general, acylphosphine oxides (Z = 0) are synthesized in accordance with the literature (see, for example, EP-A 7508 and EP-A 62839) by converting alkoxyphosphines and acid chlorides to the present system in accordance with
Figure imgf000038_0001
Figure imgf000038_0001
Die beschriebene Syntheseroute ist für die Herstellung der erfindungsgemäßen, funktionalisierten Derivate jedoch ungeeignet. Sie führt zu Undefinierten Produkten, wenn R' und R' ' nicht gleich sind.However, the synthesis route described is unsuitable for the production of the functionalized derivatives according to the invention. It leads to undefined products if R 'and R' 'are not the same.
Ferner können die Reste R' und R' ' keine Funktionalitäten tolerieren, die mit einem Säurechlorid R1(C0)C1 reagieren, wie z.B. Hydroxy- oder Aminofunktionen.Furthermore, the radicals R 'and R''cannot tolerate functionalities which react with an acid chloride R 1 (C0) C1, such as, for example, hydroxyl or amino functions.
Selbst wenn es gelänge die konventionelle Synthese durch eine bislang nicht bekannte Modifizierung auf komplexere Systeme erfolgreich zu übertragen, würde bei der Verwendung von unsymmetrischen Phosphinen mit Produktmischungen zu rechnen sein, die aus der Arbusov-Umlagerung der unterschiedlichen Substituenten (R' und R' ' ) resultieren. Bei zweifacher Einbringung der gewünschten Funktionalität (R' = R'') ginge dann jedoch eine Einheit verloren; nur die Hälfte würde im Produkt verbleiben und damit synthetisch genutzt. Die Synthese verschiedener Initiatoren auf diesem Weg würde zudem jeweils eine technisch aufwendige Synthese des entsprechenden funktionalisierten Dialkoxyphosphins erfordern.Even if it were possible to successfully transfer conventional synthesis to more complex systems through a hitherto unknown modification, product asymmetry from the Arbusov rearrangement of the different substituents (R 'and R'') would have to be expected if unsymmetrical phosphines were used. result. If the desired functionality (R '= R'') were introduced twice, however, one unit would then be lost; only half would remain in the product and would therefore be used synthetically. The synthesis of different initiators in this way would also require a technically complex synthesis of the corresponding functionalized dialkoxyphosphine.
Die Synthese der erfindungsgemäßen, funktionalisierten Phosphin- derivate gelingt dagegen durch Umsetzung eines reaktiven Derivats der Formel (III) wie oben beschrieben.In contrast, the functionalized phosphine derivatives according to the invention can be synthesized by reacting a reactive derivative of the formula (III) as described above.
Die reaktive Fluchtgruppe (FG) des Moleküls (FG = Halogenid, Carboxylat, Carbonat, Carbamat, Harnstoff, Sulfonate, wie Triflat, Tosylat oder Mesylat, oder sonstige elekronenziehende Fluchtgruppe) kann leicht und schonend durch Umsetzung mit einer protonenaktiven Verbindung derivatisiert werden. Damit sind aus diesem zentralen Synthesebaustein leicht verschieden funktionalisierte Acylphosphinoxid-Derivate zugänglich, die für die unterschiedlichsten Anwendungsprofile optimiert werden können. Es können sowohl heteroatomsubstituierte Reste als auch acrylathaltige Reste eingebracht werden.The reactive escape group (FG) of the molecule (FG = halide, carboxylate, carbonate, carbamate, urea, sulfonates, such as triflate, tosylate or mesylate, or other electron-withdrawing escape group) can be easily and gently derivatized by reaction with a proton-active compound. This makes it possible to access slightly differently functionalized acylphosphine oxide derivatives from this central synthesis building block, which can be optimized for a wide variety of application profiles. Both heteroatom-substituted residues and acrylate-containing residues can be introduced.
/ R2 / R 2
R ll FGR ll FG
00
Figure imgf000039_0001
Figure imgf000039_0001
Darin stehe R für eine beliebige der oben angeführten Substitutionen und HetH für beliebige protonenaktive Gruppen.R stands for any of the above substitutions and HetH for any proton-active groups.
Diese Synthese ist allgemein anwendbar und toleriert die ver- schiedensten funktioneilen Gruppen (z. B. Alkohole, Amine, Ether, Acrylate und Methacrylate, Olefine, etc.). Dadurch sind in einem einzigen Schritt, ausgehend von einer zentralen Verbindung (III) , die verschiedensten abgeleiteten funktionalisierten Photoinitiatoren zugänglich:
Figure imgf000040_0001
This synthesis is generally applicable and tolerates a wide variety of functional groups (eg alcohols, amines, ethers, acrylates and methacrylates, olefins, etc.). As a result, in a single step, starting from a central compound (III), a wide variety of derived functionalized photoinitiators are accessible:
Figure imgf000040_0001
(1 : : 2 Produkt)(1:: 2 product)
Figure imgf000040_0002
: 1 Produkt)
Figure imgf000040_0002
: 1 product)
Darin stehe R für eine beliebige der oben angeführten Substitutionen und die Zahlen n für beliebige der oben beschriebenen Zah- len.Here R stands for any of the substitutions listed above and the numbers n for any of the numbers described above.
Insbesondere sind durch die schonende Umsetzung Verbindungen mit Heteroatomsubstitution zugänglich die in verschiedenen Lackmischungen besser löslich oder verträglich sind, aufgrund der Pola- rität der Kette oder einem höheren Molekulargewicht mit mehreren potentiellen Radikalzentren weniger migrierbar oder auch aufgrund einer copolymerisierbaren Struktureinheit im Polymer einbaubar sind.In particular, the gentle reaction makes it possible to obtain compounds with heteroatom substitution which are more soluble or compatible in various lacquer mixtures, are less migrable with several potential radical centers owing to the polarity of the chain or a higher molecular weight, or can also be incorporated in the polymer due to a copolymerizable structural unit.
Ein weiterer alternativer Zugang zu funktionalisierten Acylphosp- hinoxiden ergibt sich aus der Acylphosphinsäure . Diese kann mit verschiedenen Epoxiden zu den abgeleiteten Hydroxyalkylderivaten ungesetzt werden.Another alternative approach to functionalized acylphosphine oxides results from acylphosphinic acid. This can be converted to the derived hydroxyalkyl derivatives using various epoxides.
Sowohl die Acylphosphinsäure, deren Anionen als auch deren Hydro- xyalkylderivate können mit reaktiven Substraten [z. B. Isocyanate (Monoisocyanate, Diisocyanate, wie z.B. Methandiphenyldiisocyanat (MDI) , Hexamethylendiisocyanat (HDI) , Toluylendiisocyanat (TDI) , sowohl als 2,4- als auch als 2,6-Isomer, sowie Gemische davon, Isophorondiisocyanat (IPDI) , sowohl Mono- als auch Diadukte, und Polyisocyanate) , Säurechloride, Alkylenoxide, Epichlorhydrin u.a.] funktionalisiert werden. Die in Monoaddukten noch vorhandene Isocyanat-Gruppierung kann zur weiteren Funktionalisierung genutzt werden. Auch eine Hydrolyse zu Photoinitiatoren mit einer primären Aminfunktionalität und damit die Michael-Addition an die Acrylat-Funktionalität eines strahlungshärtbaren Harzes (siehe z.B. EP-A 950 219) ist möglich. Über diese Syntheseroute sind ebenfalls Acrylat-funktionalisierte Acylphosphinoxid-Photoinitiatoren erhältlich.Both acylphosphinic acid, its anions and its hydroxyalkyl derivatives can be reacted with reactive substrates [e.g. B. isocyanates (monoisocyanates, diisocyanates, such as methane diphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), both as 2,4- and 2,6-isomer, and mixtures thereof, isophorone diisocyanate (IPDI), both Mono- and diaducts, and polyisocyanates), acid chlorides, alkylene oxides, epichlorohydrin, etc.] can be functionalized. The isocyanate grouping still present in monoadducts can be used for further functionalization. Hydrolysis to photoinitiators with a primary amine functionality and thus Michael addition to the acrylate functionality of a radiation-curable resin (see e.g. EP-A 950 219) is possible. Acrylate-functionalized acylphosphine oxide photoinitiators are also available via this synthetic route.
Figure imgf000041_0001
Figure imgf000041_0001
Weiterhin sind Gegenstand der Erfindung Verbindungen, die durch Umsetzung von (I) oder (IV) , bevorzugt durch Umsetzung von (IV) , mit reaktiven Gruppen enthaltenden Verbindungen erhältlich sind. Reaktive Gruppen sind solche, die mit der Gruppe RG oder -Het2"H der Verbindungen (I) oder (IV) eine chemische Bindung einzugehen vermögen.The invention furthermore relates to compounds which can be obtained by reacting (I) or (IV), preferably by reacting (IV), with compounds containing reactive groups. Reactive groups are those which are able to form a chemical bond with the group RG or -Het 2 "H of the compounds (I) or (IV).
Dies können beispielsweise Isocyanat-, Epoxid-, Anhydrid-, Säurechlorid-, Ester-, Säure-, Carbonat-, Aldehyd-, α, ß-ungesättigte Carbonyl-, Chloralkyl-, Bromalkyl-, Iodalkyl- oder Nitrilgruppen sein.These can be, for example, isocyanate, epoxy, anhydride, acid chloride, ester, acid, carbonate, aldehyde, α, β-unsaturated carbonyl, chloroalkyl, bromoalkyl, iodoalkyl or nitrile groups.
Der Begriff "Säure" steht hier für beispielsweise Carbonsäuren oder Sulfonsäuren, bevorzugt Carbonsäuren.The term "acid" here means, for example, carboxylic acids or sulfonic acids, preferably carboxylic acids.
Solche reaktive Gruppen enthaltenden Verbindungen können bei- spielsweise sein 1, 6-Hexamethylendiisocyanat (HDI), 2,4- und 2,6- Toluoldiisocyanat (TDI) , 4 , 4 ' -Methylendi (phenylisocyanat) (MDI) , Isophorondiisocyanat (IPDI) , Bisphenol A mono- und -diglycidylether, Bisphenol B mono- und -diglycidylether, Bisphenol F mono- und -diglycidylether, 2 , 2-Bis (4-hydroxycyclohexyl) propan mono- und -diglycidylether, Maleinsäureanhydrid, Phthalsäureanhydrid, ε-Caprolacton, ε-Caprolactam, Vinyloxiran, Epichlorhydrin sowie Adipinsäure, (Meth) acrylsäure, Crotonsäure, Maleinsäure, Fumar- säure und die Ester dieser Säuren.Compounds containing such reactive groups can be, for example, 1,6-hexamethylene diisocyanate (HDI), 2,4- and 2,6-toluenediisocyanate (TDI), 4,4'-methylenedi (phenyl isocyanate) (MDI), isophorone diisocyanate (IPDI) , Bisphenol A mono- and diglycidyl ether, bisphenol B mono- and diglycidyl ether, bisphenol F mono- and diglycidyl ether, 2,2-bis (4-hydroxycyclohexyl) propane mono- and diglycidyl ether, maleic anhydride, phthalic anhydride, ε-caprol ε-caprolactam, vinyloxirane, epichlorohydrin and Adipic acid, (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid and the esters of these acids.
Die so erhältlichen Verbindungen sind beispielsweise (Formel (Va - c))The compounds obtainable in this way are, for example (formula (Va-c))
Figure imgf000042_0001
Figure imgf000042_0001
Figure imgf000042_0002
Figure imgf000042_0002
Figure imgf000042_0003
Figure imgf000043_0001
Figure imgf000042_0003
Figure imgf000043_0001
worinwherein
R11 beispielsweise 1,6-Hexylen, 3 , 5 , 5-Trimethyl-l , 3-cyclohexylen, 1-Methyl-2 , 4-phenyl, 1-Methyl-2 , 6-phenyl , 4 , 4 ' -Diphenylmethy- len, 2 , 4 '-Diphenylmethylen oder 2 ' , 4-Diphenylmethylen undR 11, for example 1,6-hexylene, 3, 5, 5-trimethyl-l, 3-cyclohexylene, 1-methyl-2, 4-phenyl, 1-methyl-2, 6-phenyl, 4, 4 '-diphenylmethy- len, 2, 4 '-diphenylmethylene or 2', 4-diphenylmethylene and
R11 Wasserstoff oder MethylR 11 is hydrogen or methyl
sein kann.can be.
Insbesondere sind von den Acyl- und Bisacylphosphinderivaten, die durch die Formeln (Va bis c) beschrieben sind, die folgenden Individuen V-l bis V-390 bevorzugt, in denen die Reste in Formel (Va bis c) die folgenden Bedeutungen haben:In particular, of the acyl and bisacylphosphine derivatives described by the formulas (Va to c), the following individuals V-1 to V-390 are preferred, in which the radicals in formula (Va to c) have the following meanings:
Figure imgf000043_0002
Figure imgf000044_0001
Figure imgf000043_0002
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000068_0001
TMP : 2,4, 6-Trimethyl-l-phenylTMP: 2,4,6-trimethyl-1-phenyl
DMP : 2 , 6-Dimethyl-l-phenylDMP: 2,6-dimethyl-1-phenyl
DMOP : 2 , 6-Dirnethoxy-1-phenylDMOP: 2,6-dirthethoxy-1-phenyl
DCP: 2, 6-Dichlor-l-phenylDCP: 2,6-dichloro-1-phenyl
TMB: 2,4, 6-TrimethylbenzoylTMB: 2,4,6-trimethylbenzoyl
Ph : PhenylPh: phenyl
EtO : EthoxyEtO: ethoxy
Wie oben ausgeführt, sind auch solche Individuen aus der Tabelle bevorzugt, bei denen R2 ' 4-Methylphenyl, 4-Methoxyphenyl, 4-Chlor- phenyl, Methoxy, n-Propoxy, iso-Propoxy, n-Butoxy, seTc-Butoxy, so-Butoxy oder tert-Butoxy sind.As stated above, preference is also given to those individuals from the table in whom R 2 ′ 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl, methoxy, n-propoxy, isopropoxy, n-butoxy, seTc-butoxy, are so-butoxy or tert-butoxy.
Wie oben ausgeführt, sind auch solche Individuen aus der Tabelle bevorzugt, bei denen R1' ortho-substituiert sind, beispielsweise 2-Methylphenyl, 2 , 6-Dimethyl-l-phenyl, 2-Methoxyphenyl, 2,6-Dime- thoxy-1-phenyl , 2 , 6-Dichlor-l-phenyl oder 2-Chlorphenyl . Die geringe Migration der erfindungsgemäßen Verbindungen beruht auf Wechselwirkungen von polaren Gruppen in den Verbindungen mit der strahlungshärtbaren oder strählungsgehärteten Masse. Durch diese Wechselwirkungen werden die erfindungsgemäß Verbindungen stärker im Polymerisat gebunden, als dies bei den eingangs erwähnten handelsüblichen Photoinitiatoren der Fall ist.As stated above, preference is also given to those individuals from the table in whom R 1 'is ortho-substituted, for example 2-methylphenyl, 2,6-dimethyl-1-phenyl, 2-methoxyphenyl, 2,6-dimethyl- 1-phenyl, 2, 6-dichloro-l-phenyl or 2-chlorophenyl. The low migration of the compounds according to the invention is based on interactions of polar groups in the compounds with the radiation-curable or radiation-hardened mass. As a result of these interactions, the compounds according to the invention are more strongly bound in the polymer than is the case with the commercially available photoinitiators mentioned at the outset.
Polare Gruppen, die Wechselwirkungen eingehen können sind solche, die z.B. elektrostatische Wechselwirkungen, Dipol-Dipol-Wechsel- Wirkungen, Induktions- (Debye-) Wechselwirkungen oder Wasserstoffbrückenbindungen eingehen können.Polar groups that can interact are those that e.g. electrostatic interactions, dipole-dipole interactions, induction (Debye) interactions or hydrogen bonds.
Dies sind beispielsweise Hydroxy-, Mono-, Di- und unsubstituierte Amino-, Carbonsäure-, Sulfonsäure-, Ammonium-, Carboxylat-, Sul- fonat- oder Amidgruppen, bevorzugt Hydroxy-, Mono-, Di- und unsubstituierte Amino-, Carbonsäure-, Ammonium-, Carboxylat- oder Sulfonatgruppen.These are, for example, hydroxyl, mono-, di- and unsubstituted amino, carboxylic acid, sulfonic acid, ammonium, carboxylate, sulfonate or amide groups, preferably hydroxy, mono-, di- and unsubstituted amino, carboxylic acid -, Ammonium, carboxylate or sulfonate groups.
Dies ist verstärkt bei den Photoinitiatoren, die einbaubar sind, z.B. solche, die radikalisch polymerisierbare Mehrfachbindungen oder reaktive Zentren tragen.This is intensified with the photoinitiators that can be installed, e.g. those which carry radically polymerizable multiple bonds or reactive centers.
Reaktive Zentren sind solche, die mit Gruppen wie Hydroxy-, Mono- und unsubstituierte Amino-, Carbonsäure-, Sulfonsäure-, Carboxy- lat-, Sulfonat- oder Amidgruppen, in der strahlungshärtbaren Masse eine chemische Bindung einzugehen vermögen.Reactive centers are those which are able to form a chemical bond in the radiation-curable composition with groups such as hydroxy, mono- and unsubstituted amino, carboxylic acid, sulfonic acid, carboxylate, sulfonate or amide groups.
Diese reaktiven Zentren können beispielsweise Isocyanat-, Epoxid-, Anhydrid-, Säurechlorid-, Ester-, Säure-, Carbonat-, Alde- hyd-, α, ß-ungesättigte Carbonyl-, Chloralkyl-, Bromalkyl-, Iodal- kyl- oder Nitrilgruppen sein.These reactive centers can be, for example, isocyanate, epoxy, anhydride, acid chloride, ester, acid, carbonate, aldehyde, α, β-unsaturated carbonyl, chloroalkyl, bromoalkyl, iodoalkyl or Be nitrile groups.
Bevorzugt sind Isocyanat-, Epoxid-, Ester-, Säure-, Carbonat-, Aldehyd- und α, ß-ungesättigte Carbonylgruppen. Besonders bevorzugt sind Isocyanat-, Epoxid-, Ester- und α, ß-ungesättigte Carbonylgruppen.Isocyanate, epoxy, ester, acid, carbonate, aldehyde and α, β-unsaturated carbonyl groups are preferred. Isocyanate, epoxy, ester and α, β-unsaturated carbonyl groups are particularly preferred.
Ganz besonders bevorzugt sind Isocyanat-, Epoxid- und α, ß-ungesättigte Carbonylgruppen.Isocyanate, epoxy and α, β-unsaturated carbonyl groups are very particularly preferred.
So können auch die erfindungsgemäßen Acyl- und Bisacylphosphinde- rivate der Formel (IV) eingebaut werden, wenn in der strahlungs- härtbaren Masse die entsprechenden komplementären Gruppen vorhanden sind, die mit der Gruppe -Het2-H reagieren können, z.B. Iso- cyanat, cc,ß-ungesättigte CarbonylVerbindungen, Epoxide und dergleichen. Umgekehrt können die erfindungsgemäßen Verbindungen der Formel (Va bis c) in strahlungshärtbaren Massen verarbeitet werden, wenn die Isocyanat- oder Epoxyfunktionen mit polaren Gruppen in der Masse reagieren.Thus, the acyl and bisacylphosphine derivatives of the formula (IV) according to the invention can also be incorporated if the corresponding complementary groups which can react with the group -Het 2 -H, for example isocyanate, are present in the radiation-curable composition. cc, β-unsaturated carbonyl compounds, epoxies and the like. Conversely, the compounds of the formula (Va to c) according to the invention can be processed in radiation-curable compositions if the isocyanate or epoxy functions react with polar groups in the composition.
Beide Mechanismen bewirken eine Verankerung der erfindungsgemäßen Verbindungen in der strahlungshärtbaren Masse und mithin eine geringere Migration.Both mechanisms cause the compounds according to the invention to be anchored in the radiation-curable composition and consequently to reduce migration.
Selbstverständlich können Acyl- und Bisacylphosphinderivate der Formel (III) auch mit Verbindungen umgesetzt werden, die eine andere Photoinitiatorgrundstuktur und reaktive Gruppen enthalten, beispielsweise Benzophenone, Acetophenone, Hydroxyacetophenone, Phenylglyoxylsäuren, Phenylglyoxylsäureester, Anthrachinone oder Benzoine.Of course, acyl and bisacylphosphine derivatives of the formula (III) can also be reacted with compounds which contain a different photoinitiator basic structure and reactive groups, for example benzophenones, acetophenones, hydroxyacetophenones, phenylglyoxylic acids, phenylglyoxylic acid esters, anthraquinones or benzoins.
Besonders sei die Umsetzung von (III) mit 4-Hydroxyacetophenon, 4-Hydroxybenzophenon, 2-Hydroxy-4-methoxy-benzophenon, 4-Amin- obenzophenon, 2-Hydroxy-2 , 2-dimethylacetophenon, 4'- (2 ' '-Hydro- xyethoxy) -2-hydroxy-2 , 2-dimethylacetophenon oder 1-Hydroxyaceto- phenon hervorgehoben.Especially the reaction of (III) with 4-hydroxyacetophenone, 4-hydroxybenzophenone, 2-hydroxy-4-methoxy-benzophenone, 4-amine-top zophenone, 2-hydroxy-2, 2-dimethylacetophenone, 4'- (2 '' -Hydro- xyethoxy) -2-hydroxy-2, 2-dimethylacetophenone or 1-hydroxyaceto-phenone highlighted.
Dadurch entstehen als Photoinitiatoren verwendbare Verbindungen, die in verschiedenen Absorptionsbereichen absorbieren und so eine bessere Ausnutzung der eingestrahlten aktiven Energiestrahlung erlauben.This results in compounds which can be used as photoinitiators and which absorb in different absorption regions and thus allow better use of the radiated active energy radiation.
Die erfindungsgemäßen Photoinitiatoren können selbstverständlich auch im Gemisch mit anderen Photoinitiatoren verwendet werden. Dies können beispielsweise dem Fachmann bekannte Photoinitiatoren sein, z.B. solche in "Advances in Polymer Science", Volume 14, Springer Berlin 1974 oder in K. K. Dietliker, Chemistry and Technology of UV- and EB-Formulation for Coatings, Inks and Paints, Volume 3; Photoinitiators for Free Radical and Cationic Polymeri- zation, P. K. T. Oldring (Eds) , SITA Technology Ltd, London, genanntenThe photoinitiators according to the invention can of course also be used in a mixture with other photoinitiators. These can be, for example, photoinitiators known to those skilled in the art, e.g. those in "Advances in Polymer Science", Volume 14, Springer Berlin 1974 or in K.K. Dietliker, Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints, Volume 3; Photoinitiators for Free Radical and Cationic Polymerization, P.K.T. Oldring (Eds), SITA Technology Ltd, London
In Betracht kommen z.B. Mono- oder Bisacylphosphinoxide, wie sie z.B. in EP-A 7 508, EP-A 57 474, DE-A 196 18 720, EP-A 495 751 oder EP-A 615 980 beschrieben sind, beispielsweise 2,4,6-Trime- thylbenzoyldiphenylphosphinoxid (Lucirin® TPO, BASF AG) , Ethyl-2 , 4, 6-trimethylbenzoylphenylphosphinat (Lucirin® TPO L, BASF AG), Bis- (2, 4, 6-trimethylbenzoyl) -phenylphosphinoxid (Irga- cure® 819 der Firma Ciba Spezialitätenchemie) , Benzophenone, Hy- droxyacetophenone, Phenylglyoxylsäure und ihre Derivate oder Gemische dieser Photoinitiatoren. Als Beispiele seien genannt Ben- zophenon, Acetophenon, Acetonaphthochinon, Methylethylketon, Va- lerophenon, Hexanophenon, α-Phenylbutyrophenon, p-Morpholinopro- piophenon, Dibenzosuberon, 4-Morpholinobenzophenon, 4-Morpholino- deoxybenzoin, p-Diacetylbenzol, 4-Aminobenzophenon, 4'-Methoxya- cetophenon, ß-Methylanthrachinon, tert-Butylanthrachinon, Anthra- chinoncarbonysäureester, Benzaldehyd, α-Tetralon, 9-Acetylphe- nanthren, 2-Acetylphenanthren, 10-Thioxanthenon, 3-Acetylphenant- hren, 3-Acetylindol , 9-Fluorenon, 1-Indanon, 1 , 3 , 4-Triacetylben- zol, Thioxanthen-9-on, Xanthen-9-on, 2 , 4-Dimethylthioxanthon, 2 , 4-Diethylthioxanthon, 2 , 4-Di-iso-propylthioxanthon, 2,4-Dich- lorthioxanthon, Benzoin, Benzoin-isσ-butylether, Chloroxanthenon, Benzoin-tetrahydropyranylether, Benzoin-methylether, Benzoin- ethylether, Benzoin-butylether, Benzoin-iso-propylether, 7-H-Ben- zoin-methylether, Benz [de] anthracen-7-on, 1-Naphthaldehyd, 4, 4 '-Bis (dimethylamino)benzophenon, 4-Phenylbenzophenon, 4-Chlor- benzophenon, Michlers Keton, 1-Acetonaphthon, 2-Acetonaphthon, 1-Benzoylcyclohexan-l-ol , 2-Hydroxy-2 , 2-dimethylacetophenon, 2 , 2-Dimethoxy-2-phenylacetophenon, 2 , 2-Diethoxy-2-phenylacetophe- non, 1, 1-Dichloracetophenon, 1-Hydroxyacetophenon, Acetophenondi- methylketal, o-Methoxybenzophenon, Triphenylphosphin, Tri-o-To- lylphosphin, Benz [a] anthracen-7 , 12-dion, 2, 2-Diethoxyacetophenon, Benzilketale, wie Benzildi ethylketal, 2-Methyl-l- [4- (methylt- hio) phenyl] -2-morpholinopropan-l-on, Anthrachinone wie 2-Methy- lanthrachinon, 2-Ethylanthrachinon, 2-tert-Butylanthrachinon, 1-Chloranthrachinon, 2-Amylanthrachinon und 2 , 3-Butandion.For example, mono- or bisacylphosphine oxides such as are described in EP-A 7 508, EP-A 57 474, DE-A 196 18 720, EP-A 495 751 or EP-A 615 980, for example 2.4 , 6-trimethylbenzoyldiphenylphosphine oxide (Lucirin ® TPO, BASF AG), ethyl 2, 4, 6-trimethylbenzoylphenylphosphinate (Lucirin ® TPO L, BASF AG), bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (Irga cure® 819 from Ciba Specialty Chemicals), benzophenones, hydroxyacetophenones, phenylglyoxylic acid and their derivatives or mixtures of these photoinitiators. Examples include benzophenone, acetophenone, acetonaphthoquinone, methyl ethyl ketone, Va lerophenone, hexanophenone, α-phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberon, 4-morpholinobenzophenone, 4-morpholino-deoxybenzoin, p-diacetylbenzene, 4-aminobenzophenone, 4'-methoxy-anthracon, methyl-anthronone, antithephthenone, antithephthenone, antithephthenone, antithephtheno, anthracetaminophenone, - Quinone carbonate, benzaldehyde, α-tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene, 10-thioxanthenone, 3-acetylphenanthene, 3-acetylindole, 9-fluorenone, 1-indanone, 1, 3, 4-triacetylbenzene , Thioxanthene-9-one, xanthene-9-one, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-di-iso-propylthioxanthone, 2,4-dichlorothioxanthone, benzoin, benzoin isσ-butyl ether , Chloroxanthenone, benzoin tetrahydropyranyl ether, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, benzoin iso-propyl ether, 7-H-benzoin methyl ether, benz [de] anthracen-7-one, 1-naphthaldehyde, 4 , 4 '-Bis (dimethylamino) benzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, Michler's ketone, 1-acetonaphthone, 2-acetonaphthone, 1-benzoylcycloh exan-l-ol, 2-hydroxy-2, 2-dimethylacetophenone, 2, 2-dimethoxy-2-phenylacetophenone, 2, 2-diethoxy-2-phenylacetophenone, 1, 1-dichloroacetophenone, 1-hydroxyacetophenone, acetophenone di methyl ketal, o-methoxybenzophenone, triphenylphosphine, tri-o-tolylphosphine, benz [a] anthracen-7, 12-dione, 2, 2-diethoxyacetophenone, benzil ketals, such as benzil diethyl ketal, 2-methyl-l- [4- ( methylt-hio) phenyl] -2-morpholinopropan-l-one, anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone and 2, 3-butanedione.
Geeignet sind auch nicht- oder wenig vergilbende Photoinitiatoren vom Phenylglyoxalsäureestertyp, wie in DE-A 198 26 712, DE-A 199 13 353 oder WO 98/33761 beschrieben.Non-yellowing or little yellowing photoinitiators of the phenylglyoxalic acid ester type are also suitable, as described in DE-A 198 26 712, DE-A 199 13 353 or WO 98/33761.
Die erfindungsgemäßen Verbindungen der Formeln (I) oder (IV) reagieren beziehungsweise wechselwirken nach Vermischen mit der zu härtenden Masse mit deren reaktiven Zentren oder polaren Gruppen und werden so migrationsfest gebunden.The compounds of the formulas (I) or (IV) according to the invention react or interact after mixing with the mass to be hardened with their reactive centers or polar groups and are thus bound in a migration-resistant manner.
Die mit den erfindungsgemäßen, einbaubaren Photoinitiatoren hergestellten Beschichtungsmassen eignen sich besonders zur Verwendung in VerpackungsSystemen, besonders bevorzugt im Lebensmittelbereich.The coating compositions produced with the installable photoinitiators according to the invention are particularly suitable for use in packaging systems, particularly preferably in the food sector.
Geeignet sind beispielsweise solche strahlungshärtbaren Massen, die pro 100 g Substanz von 0,01 bis 1,4 mol reaktive Zentren, bevorzugt 0,05 bis 1,25, besonders bevorzugt 0,1 bis 1, ganz besonders bevorzugt 0,2 bis 0,75 mol reaktive Zentren und/oder von 0,01 bis 1,25 mol polare Gruppen, bevorzugt 0,05 bis 1,15, beson- ders bevorzugt 0,1 bis 1, ganz besonders bevorzugt 0,2 bis 0,75 mol polare Gruppen aufweisen. Bevorzugt sind solche strahlungshärtbaren Massen, die von 0,01 bis 1,25 mol, bevorzugt 0,05 bis 1,15, besonders bevorzugt 0,1 bis 1, ganz besonders bevorzugt 0,2 bis 0,75 mol Hydroxygruppen pro 100 g Substanz und/oder von 0,01 bis 0,75, bevorzugt 0,05 bis 0,66, besonders bevorzugt 0,1 bis 0,5 mol Isocyanatgruppen pro 100 g Substanz und/oder von 0,01 bis 1,4 mol, bevorzugt 0,05 bis 1,25, besonders bevorzugt 0,1 bis 1, ganz besonders bevorzugt 0,2 bis 0,75 mol Epoxidgruppen pro 100 g Substanz und/oder von 0,01 bis 1,4 mol, bevorzugt 0,05 bis 1,25, besonders bevorzugt 0,1 bis 1, ganz besonders bevorzugt 0,2 bis 0,75 mol α, ß-ungesättigte Carbonylgruppen pro 100 g Substanz aufweisen.Suitable radiation-curable compositions are, for example, those having from 0.01 to 1.4 mol of reactive centers per 100 g of substance, preferably 0.05 to 1.25, particularly preferably 0.1 to 1, very particularly preferably 0.2 to 0, 75 mol reactive centers and / or from 0.01 to 1.25 mol polar groups, preferably 0.05 to 1.15, particularly preferably 0.1 to 1, very particularly preferably 0.2 to 0.75 mol polar groups Have groups. Radiation-curable compositions are preferred which contain from 0.01 to 1.25 mol, preferably 0.05 to 1.15, particularly preferably 0.1 to 1, very particularly preferably 0.2 to 0.75 mol of hydroxyl groups per 100 g of substance and / or from 0.01 to 0.75, preferably 0.05 to 0.66, particularly preferably 0.1 to 0.5 mol of isocyanate groups per 100 g of substance and / or from 0.01 to 1.4 mol, preferably 0.05 to 1.25, particularly preferably 0.1 to 1, very particularly preferably 0.2 to 0.75 mol of epoxy groups per 100 g of substance and / or from 0.01 to 1.4 mol, preferably 0.05 to 1.25, particularly preferably 0.1 to 1, very particularly preferably 0.2 to 0.75 mol of α, β-unsaturated carbonyl groups per 100 g of substance.
Die Bindung der erfindungsgemäßen Acyl- und Bisacylphosphinderi- vate der Formeln (I) oder (IV) an die reaktiven Zentren oder po- laren Gruppen erfolgt in der Regel bei einer Temperatur zwischen Raumtemperatur und der Härtungstemperatur der strahlungshärtbaren Masse. Typische Temperaturen liegen bei 40 - 120 °C, bevorzugt 50 - 110 °C und besonders bevorzugt 60 - 100 °C.The acyl and bisacylphosphine derivatives of the formulas (I) or (IV) according to the invention are generally bound to the reactive centers or polar groups at a temperature between room temperature and the curing temperature of the radiation-curable composition. Typical temperatures are 40-120 ° C, preferably 50-110 ° C and particularly preferably 60-100 ° C.
Im Verlauf des Härtungs- beziehungsweise Bindungsprozesses kann die Temperatur gleichbleiben oder angehoben werden.The temperature can remain the same or be raised during the course of the hardening or bonding process.
Die Dauer der thermischen Behandlung liegt in der Regel zwischen wenigen Minuten und mehreren Stunden, beispielsweise von 1 Minute bis 5 Stunden, bevorzugt 2 Minuten bis 3 Stunden, besonders bevorzugt 5 Minuten bis 2 Stunden und insbesondere von 10 Minuten bis 1 Stunde.The duration of the thermal treatment is generally between a few minutes and several hours, for example from 1 minute to 5 hours, preferably 2 minutes to 3 hours, particularly preferably 5 minutes to 2 hours and in particular from 10 minutes to 1 hour.
Gegenstand der Erfindung sind demzufolge auch strahlungshärtbare Massen, die durch Umsetzung mindestens eines Acyl- und Bisacyl- phosphinderivates gemäß Formel (I) oder (IV) oder hergestellt nach einem erfindungsgemäßen Verfahren mit einer mindestens ein reaktives Zentrum und/oder mindestens eine polare Gruppe enthaltenden strahlungshärtbaren Zusammensetzung erhältlich sind.The invention accordingly also relates to radiation-curable compositions which comprise radiation-curable compositions which contain at least one reactive center and / or at least one polar group by reacting at least one acyl and bisacylphosphine derivative of the formula (I) or (IV) or prepared by a process according to the invention Composition are available.
Ein weiterer Gegenstand der vorliegenden Erfindung sind strahlungshärtbare Massen, enthaltend einen erfindungsgemäßen Photoinitiator.Another object of the present invention are radiation-curable compositions containing a photoinitiator according to the invention.
Strahlungshärtbare Zusammensetzungen enthalten typischerweiseRadiation curable compositions typically contain
(A) mindestens eine polymerisierbare Verbindung mit einer oder mehreren copolymerisierbaren, ethylenisch ungesättigten Gruppen,(A) at least one polymerizable compound with one or more copolymerizable, ethylenically unsaturated groups,
(B) gegebenenfalls Reaktiwerdünner, (C) mindestens einen erfindungsgemäßen Photoinitiator und gegebenenfalls mindestens einen weiteren an sich bekannten Photoinitiator sowie(B) optionally reactive diluent, (C) at least one photoinitiator according to the invention and optionally at least one further photoinitiator known per se and
(D) gegebenenfalls weitere lacktypische Additive.(D) optionally further paint-typical additives.
Typische Zusammensetzungen sind beispielsweiseTypical compositions are, for example
(A) 40 - 100 Gew%, bevorzugt 50 - 90, besonders bevorzugt 60 - 90 und insbesondere 60 - 80 Gew%,(A) 40-100% by weight, preferably 50-90, particularly preferably 60-90 and in particular 60-80% by weight,
(B) 0 - 60 Gew%, bevorzugt 5 - 50, besonders bevorzugt 6 - 40 und insbesondere 10 - 30 Gew%,(B) 0-60% by weight, preferably 5-50, particularly preferably 6-40 and in particular 10-30% by weight,
(C) 0,1 - 20 Gew%, bevorzugt 0,5 - 15, besonders bevorzugt 1 - 10 und insbesondere 2 - 5 Gew% sowie(C) 0.1-20% by weight, preferably 0.5-15%, particularly preferably 1-10% and in particular 2-5% by weight and
(D) 0 - 50 Gew%, bevorzugt 2 - 40, besonders bevorzugt 3 - 30 und insbesondere 5 - 20 Gew%,(D) 0-50% by weight, preferably 2-40, particularly preferably 3-30 and in particular 5-20% by weight,
mit der Maßgabe, daß die Summe immer 100 Gew% beträgt.with the proviso that the sum is always 100% by weight.
In speziellen Anwendungen kann der Anteil an lacktypischen Additiven (D) bis zu 90 Gew% betragen, in diesem Fall verringern sich die Anteile der anderen Komponenten entsprechend.In special applications, the proportion of paint additives (D) can be up to 90% by weight, in this case the proportion of the other components is reduced accordingly.
Als Verbindungen (A) kommen strahlungshärtbare, radikalisch polymerisierbare Verbindungen mit mehreren, d.h. mindestens zwei, co- polymerisierbaren, ethylenisch ungesättigten Gruppen in Betracht.As compounds (A) there are radiation-curable, free-radically polymerizable compounds with several, i.e. at least two, copolymerizable, ethylenically unsaturated groups.
Bevorzugt handelt es sich bei Verbindungen (A) um Vinylether- oder (Meth) acrylatverbindungen, besonders bevorzugt sind jeweils die Acrylatverbindungen, d.h. die Derivate der Acrylsäure.Compounds (A) are preferably vinyl ether or (meth) acrylate compounds, particularly preferred are the acrylate compounds, i.e. the derivatives of acrylic acid.
Bevorzugte Vinylether- und (Meth) acrylat-Verbindungen (A) enthalten 2 bis 20, bevorzugt 2 bis 10 und ganz besonders bevorzugt 2 bis 6 copolymerisierbare, ethylenisch ungesättigte Doppelbindungen .Preferred vinyl ether and (meth) acrylate compounds (A) contain 2 to 20, preferably 2 to 10 and very particularly preferably 2 to 6 copolymerizable, ethylenically unsaturated double bonds.
Besonders bevorzugt sind solche Verbindungen (A) mit einem Gehalt an ethylenisch ungesättigte Doppelbindungen von 0,1 - 0,7 mol /100 g, ganz besonders bevorzugt 0,2 - 0,6 mol / 100 g.Such compounds (A) with a content of ethylenically unsaturated double bonds of 0.1-0.7 mol / 100 g are particularly preferred, very particularly preferably 0.2-0.6 mol / 100 g.
Genannt seien (Meth) acrylsäureester und insbesondere Acrylsäuree- ster sowie Vinylether von mehrfunktionellen, gegebenenfalls alko- xylierten Alkoholen, (Meth) acrylsäureester oder Vinylether von Polyesterolen, Polyetherol (meth) acrylate und Urethan- oder Epoxid (meth) acrylate oder -vinylether.Mention should be made of (meth) acrylic acid esters and in particular acrylic acid esters and vinyl ethers of polyfunctional, optionally alkoxylated alcohols, (meth) acrylic acid esters or vinyl ethers of Polyesterols, polyetherol (meth) acrylates and urethane or epoxy (meth) acrylates or vinyl ethers.
Als Reaktiwerdünner (Verbindungen (B) ) kommen radikalisch poly- merisierbare Verbindungen, bevorzugt strahlungshärtbare, mit einer ethylenisch ungesättigten, copolymerisierbaren Gruppe in Betracht, oder Gemische davon.Suitable reactive diluents (compounds (B)) are free-radically polymerizable compounds, preferably radiation-curable compounds, with an ethylenically unsaturated, copolymerizable group, or mixtures thereof.
Genannt seien z.B. α,ß-ungesättigte Carbonsäuren, Cι-C20-Al- kyl (meth) acrylate, Vinylaromaten mit bis zu 20 C-Atomen, Vinyle- ster von bis zu 20 C-Atomen enthaltenden Carbonsäuren, ethylenisch ungesättigte Nitrile, Vinylether von 1 bis 10 C-Atome enthaltenden Alkoholen und aliphatischen Kohlenwasserstoffen mit 2 bis 8 C-Atomen und 1 oder 2 Doppelbindungen.Examples include α, β-unsaturated carboxylic acids, C 1 -C 20 alkyl (meth) acrylates, vinyl aromatics with up to 20 C atoms, vinyl esters of carboxylic acids containing up to 20 C atoms, ethylenically unsaturated nitriles, vinyl ethers of alcohols containing 1 to 10 carbon atoms and aliphatic hydrocarbons with 2 to 8 carbon atoms and 1 or 2 double bonds.
Der Begriff (Meth) acrylsäure wird im Rahmen dieser Schrift für Acrylsäure und Methacrylsäure verwendet.The term (meth) acrylic acid is used in the context of this document for acrylic acid and methacrylic acid.
Als α,ß-ungesättigte Carbonsäuren können beispielsweise Acryl- säure, Methacrylsäure, Maleinsäure oder deren Halbester, 3-Acry- loxypropionsäure, Maleinsäureanhydrid, Fumarsäure oder deren Halbester oder Crotonsäure verwendet werden.Examples of α, β-unsaturated carboxylic acids which can be used are acrylic acid, methacrylic acid, maleic acid or its half-ester, 3-acrylicoxypropionic acid, maleic anhydride, fumaric acid or its half-ester or crotonic acid.
Als (Meth) acrylsäurealkylester bevorzugt sind solche mit einem Cι-Cιo-Alkylrest, wie Methylmethacrylat, Methylacrylat und Ethyla- crylat .Preferred (meth) acrylic acid alkyl esters are those having a C 1 -C 8 -alkyl radical, such as methyl methacrylate, methyl acrylate and ethyl acrylate.
Insbesondere sind auch Mischungen der (Meth) acrylsäurealkylester geeignet.Mixtures of the (meth) acrylic acid alkyl esters are also particularly suitable.
Vinylester von Carbonsäuren mit 1 bis 20 C-Atomen sind z.B. Vi- nyllaurat, Vinylstearat, Vinylpropionat und Vinylacetat.Vinyl esters of carboxylic acids with 1 to 20 C atoms are e.g. Vinyl laurate, vinyl stearate, vinyl propionate and vinyl acetate.
Als vinylaromatische Verbindungen kommen z.B. Vinyltoluol, α-Bu- tylstyrol, 4-n-Butylstyrol, 4-n-Decylstyrol und vorzugsweise Sty- rol in Betracht.As vinyl aromatic compounds e.g. Vinyltoluene, α-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene are suitable.
Beispiele für Nitrile sind Acrylnitril und Methacrylnitril .Examples of nitriles are acrylonitrile and methacrylonitrile.
Geeignete Vinylether sind z.B. Vinylmethylether, Vinylisobutyle- ther, Vinylhexylether und Vinyloctylether .Suitable vinyl ethers are e.g. Vinyl methyl ether, vinyl isobutyl ether, vinyl hexyl ether and vinyl octyl ether.
Als nicht aromatische Kohlenwasserstoffe mit 2 bis 8 C-Atomen und einer oder zwei olefinischen Doppelbindungen seien Butadien, Iso- pren, sowie Ethylen, Propylen und Isobutylen genannt. Weiterhin sind N-Vinylformamid, N-Vinylpyrrolidon sowie N-Vinyl- caprolactam einsetzbar.Butadiene, isoprene, as well as ethylene, propylene and isobutylene may be mentioned as non-aromatic hydrocarbons having 2 to 8 carbon atoms and one or two olefinic double bonds. N-vinylformamide, N-vinylpyrrolidone and N-vinylcaprolactam can also be used.
Als lacktypische Additive (D) können beispielsweise Antioxidan- tien, Oxidationsinhibitoren, Stabilisatoren, Aktivatoren (Beschleuniger) , Füllmittel, Pigmente, Farbstoffe, Entgasungsmittel, Glanzmittel, antistatische Agentien, Flammschutzmittel, Verdik- ker, thixotrope Agentien, Verlaufshilfsmittel, Bindemittel, Anti- schaummittel, Duftstoffe, oberflächenaktive Agentien, Viskosi- tätsmodifikatoren, Weichmacher, Plastifizierer, klebrigmachende Harze (Tackifier) , Chelatbildner oder Verträglichkeitsmittel (compatibilizer) verwendet werden.Antioxidants, oxidation inhibitors, stabilizers, activators (accelerators), fillers, pigments, dyes, degassing agents, gloss agents, antistatic agents, flame retardants, thickeners, thixotropic agents, flow control agents, binders, antifoams, for example, can be used as typical paint additives (D) , Fragrances, surface-active agents, viscosity modifiers, plasticizers, plasticizers, tackifying resins (tackifiers), chelating agents or compatibilizers.
Die Beschichtung von Substraten mit den strahlungshärtbaren Zu- sammensetzungen erfolgt nach üblichen, dem Fachmann bekanntenThe substrates with the radiation-curable compositions are coated in accordance with customary methods known to the person skilled in the art
Verfahren, wobei man wenigstens eine erfindungsgemäße strahlungshärtbare Zusammensetzunge, beispielsweise in Form einer Dispersion oder auch ohne Lösungsmittel, auf das zu beschichtende Substrat in der gewünschten Stärke aufbringt und die flüchtigen Be- standteile der Dispersion, gegebenenfalls unter Erhitzen, entfernt. Dieser Vorgang kann gewünschtenfalls ein- oder mehrfach wiederholt werden.Process in which at least one radiation-curable composition according to the invention, for example in the form of a dispersion or without solvent, is applied to the substrate to be coated in the desired thickness and the volatile constituents of the dispersion are removed, if appropriate with heating. If desired, this process can be repeated one or more times.
Das Aufbringen auf das Substrat kann in bekannter Weise, z. B. durch Spritzen, Sprühen, Eintauchen, Spachteln, Rakeln, Airblade, Bürsten, Rollen, Walzen oder Gießen erfolgen. Die Beschichtungs- stärke liegt in der Regel in einem Bereich von etwa 3 bis 1000 g/m2 und vorzugsweise 10 bis 200 g/m2.The application to the substrate can in a known manner, for. B. by spraying, spraying, dipping, filling, knife coating, airblade, brushing, rolling, rolling or pouring. The coating thickness is generally in a range from about 3 to 1000 g / m 2 and preferably 10 to 200 g / m 2 .
Weiterhin wird ein Verfahren zum Beschichten von Substraten offenbart, bei dem man eine Beschichtungsmasse, enthaltend einen erfindungsgemäßen Stoff, gegebenenfalls als Lackformulierung mit weiteren lacktypischen Additiven und/oder thermisch härtbaren Harzen versetzt, auf das Substrat aufbringt, gegebenenfalls trocknet, bei der oben angegebenen Härtungstemperatur thermisch behandelt und anschließend, gegebenenfalls bei Temperaturen bis zur Höhe der Härtungstemperatur, mit aktiver Strahlung unter Sauerstoffhaltiger Atmosphäre, wie z.B. Luft, oder bevorzugt unter Inertgas härtet .Furthermore, a method for coating substrates is disclosed, in which a coating composition containing a substance according to the invention, optionally in the form of a paint formulation with other paint-typical additives and / or thermally curable resins, is applied to the substrate, optionally dried, thermally at the curing temperature specified above treated and then, optionally at temperatures up to the curing temperature, with active radiation in an oxygen-containing atmosphere, such as Air, or preferably cures under inert gas.
Das Verfahren zum Beschichten von Substraten kann auch so durchgeführt werden, daß nach dem Aufbringen der erfindungsgemäßen Mischung oder Lackformulierung zunächst mit aktiver Energiestrahlung unter sauerstoffaltiger Atmosphäre, wie z.B. Luft, oder be- vorzugt unter Inertgas gehärtet und anschließend bei der Härtungstemperatur thermisch behandelt wird. Thermische und Strahlungshärtung kann selbstverständlich auch parallel erfolgen.The process for coating substrates can also be carried out in such a way that, after the mixture or coating formulation according to the invention has been applied, it is first cured with active energy radiation in an oxygen-containing atmosphere, such as air, or preferably under an inert gas, and then thermally treated at the curing temperature. Thermal and radiation curing can of course also take place in parallel.
Die Härtung der auf dem Substrat gebildeten Filme kann gewünsch- tenfalls ausschließlich thermisch erfolgen. Im allgemeinen härtet man die Beschichtungen jedoch sowohl durch Bestrahlung mit energiereicher Strahlung als auch thermisch.If desired, the films formed on the substrate can only be cured thermally. In general, however, the coatings are cured both by irradiation with high-energy radiation and thermally.
Gegebenenfalls kann, wenn mehrere Schichten des Beschichtungsmit- tels übereinander aufgetragen werden, nach jedem Beschichtungs- vorgang eine thermische und/oder Strahlungshärtung erfolgen.If necessary, if several layers of the coating agent are applied one above the other, thermal and / or radiation curing can take place after each coating process.
Beispiele für aktive Energiestrahlen sind ultraviolette, Röntgen- und Elektronenstrahlen, bevorzugt sind ultraviolette und Elektro- nenstrahlen.Examples of active energy rays are ultraviolet, X-ray and electron beams, ultraviolet and electron beams are preferred.
Weiterhin kann die Beschichtung von Substraten, auch wie folgt erfolgen, wobei manFurthermore, the coating of substrates can also be carried out as follows, where:
i) ein Substrat mit einer erfindungsgemäßen Mischung, wie zuvor beschrieben, beschichtet,i) coating a substrate with a mixture according to the invention, as described above,
ii) flüchtige Bestandteile der erfindungsgemäßen Mischung zurii) volatile constituents of the mixture according to the invention for
Filmbildung unter Bedingungen entfernt, bei denen der Initia- tor (C) im wesentlichen noch keine freien Radikale ausbildet,Removed film formation under conditions in which the initiator (C) essentially does not form any free radicals,
iii) gegebenenfalls den in Schritt ii) gebildeten Film mit energiereicher Strahlung bestrahlt, wobei der Film vorgehärtet wird, und anschließend gegebenenfalls den mit dem vorgehärte- ten Film beschichteten Gegenstand mechanisch bearbeitet oder die Oberfläche des vorgehärteten Films mit einem anderen Substrat in Kontakt bringt,iii) optionally irradiating the film formed in step ii) with high-energy radiation, the film being prehardened, and then, if appropriate, mechanically processing the object coated with the prehardened film or bringing the surface of the precured film into contact with another substrate,
iv) den Film thermisch endhärtet.iv) thermally cures the film.
Dabei können die Schritte iv) und iii) auch in umgekehrter Reihenfolge durchgeführt, d. h. der Film kann zuerst thermisch und dann mit energiereicher Strahlung gehärtet werden.Steps iv) and iii) can also be carried out in the reverse order. H. the film can first be cured thermally and then with high-energy radiation.
Typische Härtungstemperaturen liegen bei 40 - 120 °C, bevorzugt 50 - 110 °C und besonders bevorzugt 60 - 100 °C.Typical curing temperatures are 40-120 ° C, preferably 50-110 ° C and particularly preferably 60-100 ° C.
Im Verlauf des Härtungsprozesses kann die Temperatur gleichbleiben oder angehoben werden. Die Härtungsdauer liegt in der Regel zwischen wenigen Minuten und mehreren Stunden, beispielsweise von 1 Minute bis 5 Stunden, bevorzugt 2 Minuten bis 3 Stunden, besonders bevorzugt 5 Minuten bis 2 Stunden und insbesondere von 10 Minuten bis 1 Stunde.The temperature can remain the same or be raised during the course of the hardening process. The curing time is generally between a few minutes and several hours, for example from 1 minute to 5 hours, preferably 2 minutes to 3 hours, particularly preferably 5 minutes to 2 hours and in particular from 10 minutes to 1 hour.
Als Strahlungsquellen für die Strahlungshärtung geeignet sind z.B. Quecksilber-Niederdruckstrahler, -Mitteldruckstrahler mit Hochdruckstrahler sowie Leuchtstoffröhren, Impulsstrahier, Me- tallhalogenidstrahler, Xenonlampen, elektrodenlose Entladungslam- pen, Kohlebogenlampen, Elektronenblitzeinrichtungen, wodurch eine Strahlungshärtung ohne Photoinitiator möglich ist, oder Excimer- strahler. Die Strahlungshärtung erfolgt durch Einwirkung energiereicher Strahlung, also UV-Strahlung oder Tageslicht, vorzugsweise Licht im Wellenlängenbereich von λ=150 bis 700 nm, besonders bevorzugt von λ=200 bis 500 nm und ganz besonders bevorzugt λ=250 bis 400 nm, oder durch Bestrahlung mit energiereichen Elektronen (Elektronenstrahlung; 50 bis 1000 keV, bevorzugt 100 bis 500 und besonders bevorzugt 150 bis 300 keV) mit Vorrichtungen z.B. vom Cockroft-Walton-Typ, van-de-Graaff-Typ oder Resonanztyp. Als Strahlungsquellen dienen beispielsweise Hochdruckquecksilberdampflampen, Laser, gepulste Lampen (Blitzlicht) , Halogenlampen oder Excimerstrahler . Die üblicherweise zur Vernetzung ausreichende Strahlungsdosis bei UV-Härtung liegt im Bereich von 80 bis 3000 mJ/cm2.Suitable radiation sources for radiation curing are, for example, low-pressure mercury lamps, medium-pressure lamps with high-pressure lamps and fluorescent tubes, pulsed lamps, metal halide lamps, xenon lamps, electrodeless discharge lamps, carbon arc lamps, electron flash devices, which enables radiation curing without a photoinitiator or radiation initiator. Radiation curing takes place by exposure to high-energy radiation, that is to say UV radiation or daylight, preferably light in the wavelength range from λ = 150 to 700 nm, particularly preferably from λ = 200 to 500 nm and very particularly preferably λ = 250 to 400 nm, or by irradiation with high-energy electrons (electron radiation; 50 to 1000 keV, preferably 100 to 500 and particularly preferably 150 to 300 keV) with devices, for example of the Cockroft-Walton type, van de Graaff type or resonance type. High-pressure mercury vapor lamps, lasers, pulsed lamps (flashing light), halogen lamps or excimer lamps are used as radiation sources, for example. The radiation dose usually sufficient for crosslinking in UV curing is in the range from 80 to 3000 mJ / cm 2 .
Selbstverständlich sind auch mehrere Strahlungsquellen für die Härtung einsetzbar, z.B. zwei bis vier.Of course, several radiation sources can also be used for curing, e.g. two to four.
Diese können auch in jeweils unterschiedlichen Wellenlängeberei- chen strahlen.These can also radiate in different wavelength ranges.
Da der Chromophor des Acylphosphinoxids eine Absorptionsbande im sichtbaren Wellenlängenbereich oberhalb 400 nm aufweist, können die erfindungsgemäßen Photoinitiatoren auch mit einer Strahlungs- quelle mit einem geringen oder auch keinem UV-Anteil eingesetzt werden. Eine Tageslichthärtung ist ebenfalls möglich, wenn auch in der Regel langsamer als eine Härtung mit aktiven Energiestrahlen.Since the chromophore of acylphosphine oxide has an absorption band in the visible wavelength range above 400 nm, the photoinitiators according to the invention can also be used with a radiation source with little or no UV content. Daylight curing is also possible, although generally slower than curing with active energy rays.
Die Bestrahlung kann gegebenenfalls auch unter Ausschluß von Sauerstoff, z. B. unter Inertgas-Atmosphäre, durchgeführt werden. Als Inertgase eignen sich vorzugsweise Stickstoff, Edelgase, Kohlendioxid, oder Verbrennungsgase. Desweiteren kann die Bestrahlung erfolgen, indem die Beschichtungsmasse mit transparenten Me- dien abgedeckt wird. Transparente Medien sind z. B. Kunststofffo- lien, Glas oder Flüssigkeiten, z. B. Wasser. Besonders bevorzugt ist eine Bestrahlung in der Weise, wie sie in der DE-A 199 57 900 beschrieben ist.The radiation can optionally also in the absence of oxygen, for. B. are carried out under an inert gas atmosphere. Suitable inert gases are preferably nitrogen, noble gases, carbon dioxide or combustion gases. Irradiation can also be carried out by covering the coating material with transparent media. Transparent media are e.g. B. plastic films, glass or liquids, eg. B. water. Particularly preferred is radiation in the manner described in DE-A 199 57 900.
Ein allgemeiner Vorteil der erfindungsgemäßen Verbindungen be- steht darin, daß die Löslichkeit der Photoinitiatoren durch strukturelle Modifikationen optimal und einfach auf die verwendete strahlungshärtbare Masse abgestimmt werden kann. Ein weiterer Vorteil bei der Verwendung von z.B. pigmentierten strahlungshärtbaren Massen ist, daß die Absorption des Photoinitiators auf die verwendete strahlungshärtbare Masse abgestimmt werden kann, wenn die Absorption von herkömmlichen Acylphosphinoxiden beispielsweise durch die Pigmente verdeckt wird.A general advantage of the compounds according to the invention is that the solubility of the photoinitiators can be optimally and easily matched to the radiation-curable composition used by structural modifications. Another advantage when using e.g. pigmented radiation-curable compositions is that the absorption of the photoinitiator can be matched to the radiation-curable composition used if the absorption of conventional acylphosphine oxides is hidden, for example, by the pigments.
Mit den erfindungsgemäßen Verbindungen ist es möglich, die Wech- selwirkungen mit den strahlungshärtbarer Lacksystemen zu verbessern und so die Löslichkeit, Vermischbarkeit, Homogenisierung etc. zu optimieren. So ist es durch die Verbindungen 1-2 oder 1-21 in den Beispielen möglich, die Löslichkeit der Photoinitiatoren in Polyetherolacrylaten zu verbessern, was mit herkömmli- chen Acylphosphinoxiden nicht möglich war. Durch die Verbindungen 1-23 und 1-31 werden beispielsweise HALS-Amin-Strukturen eingebaut.With the compounds according to the invention it is possible to improve the interactions with the radiation-curable coating systems and thus to optimize the solubility, miscibility, homogenization, etc. For example, compounds 1-2 or 1-21 in the examples make it possible to improve the solubility of the photoinitiators in polyetherol acrylates, which was not possible with conventional acylphosphine oxides. The compounds 1-23 and 1-31, for example, incorporate HALS amine structures.
Die folgenden Beispiele sollen die Erfindung erläutern, ohne sie aber darauf einzuschränken.The following examples are intended to explain the invention without, however, restricting it thereto.
BeispieleExamples
Beispiel 1example 1
Trimethylbenzoylphenylphosphinsäure-NatriumsalzTrimethylbenzoylphenylphosphinic sodium salt
644 g Trimethylbenzoylphenylphosphinsäureethylester, (Lucirin® TPO-L, BASF AG) wurde in 3000 ml Ethylmethylketon vorgelegt. Zu der Lösung wurde Natriumiodid hinzugegeben. Nach 15 min wurde die homogene Lösung auf 65 °C erhitzt und 24 h gerührt. Der gelbe Niederschlag wurde abgesaugt und mit 2x500 ml Petrolether gewaschen. Der Nutschkuchen wurde im Vakuum bei 60°C getrocknet. Man isolierte 530 g (85 % der Theorie) hellgelbes Pulver.644 g of trimethylbenzoylphenylphosphinic acid ethyl ester (Lucirin® TPO-L, BASF AG) was placed in 3000 ml of ethyl methyl ketone. Sodium iodide was added to the solution. After 15 minutes, the homogeneous solution was heated to 65 ° C. and stirred for 24 hours. The yellow precipitate was filtered off and washed with 2x500 ml of petroleum ether. The filter cake was dried in vacuo at 60 ° C. 530 g (85% of theory) of light yellow powder were isolated.
31P-NMR (d6-DMS0) : δ (ppm) = 10.8 31 P NMR (d 6 -DMS0): δ (ppm) = 10.8
iH-NMR (d6-DMSO) : δ (ppm) = 2.2 (s, 6H) , 2.25 (s, 3H) , 6.6 (s, 2H) , 7.3 (m, 3H) , 7.6 (m, 2H) Beispiel 2 i H-NMR (d 6 -DMSO): δ (ppm) = 2.2 (s, 6H), 2.25 (s, 3H), 6.6 (s, 2H), 7.3 (m, 3H), 7.6 (m, 2H) Example 2
Trimethylbenzoylphenylphosphinsäuretrimethylbenzoylphenylphosphinic
5 401,55 g Natriumsalz aus Beispiel 1 wurde in 1500 ml Wasser gelöst mit 1300 ml 0,5 molarer Schwefelsäure bis der pH 1 angesäuert. Nach 1 h wurde der ausgefallene Kristallbrei abgesaugt, 2 xmit je 700 ml Wasser gewaschen und trockengesaugt. Der Nutschkuchen wurde mit 1500 ml Toluol im Wasserauskreiser azeo- 0 trop getrocknet. Die klare hellgelbe toluolische Lösung wurde bei 50°C eingeengt und die Säure aus 2150 ml Essigester umkristallisiert. Die Kristalle wurden bei 0° abgesaugt, mit Essigester gewaschen und im Vakuum bei 60 °C getrocknet.5 401.55 g of sodium salt from Example 1 was dissolved in 1500 ml of water with 1300 ml of 0.5 molar sulfuric acid until the pH 1 was acidified. After 1 h, the precipitated crystal slurry was filtered off, washed twice with 700 ml of water each time and sucked dry. The filter cake was dried azeotropically with 1500 ml of toluene in a water separator. The clear light yellow toluene solution was concentrated at 50 ° C and the acid recrystallized from 2150 ml of ethyl acetate. The crystals were filtered off with suction at 0 °, washed with ethyl acetate and dried in vacuo at 60 ° C.
5 Auswaage: 300 g (80 % der Theorie) hellgelbe Kristalle.5 scales: 300 g (80% of theory) of light yellow crystals.
31P-NMR (d6-DMS0) : δ (ppm) = 17 . 4 31 P NMR (d 6 -DMS0): δ (ppm) = 17. 4
1H-NMR ( d6-DMSO) : δ (ppm) = 2 . 1 ( s , 6H ) , 2 . 3 ( s , 3H) , 6 . 7 ( s , 2H) , 0 7 . 35 (m, 2H) , 7 . 6 (m, 1H) , 7 . 75 (m, 2H) 1 H-NMR (d 6 -DMSO): δ (ppm) = 2. 1 (s, 6H), 2. 3 (s, 3H), 6. 7 (s, 2H), 0 7. 35 (m, 2H), 7. 6 (m, 1H), 7. 75 (m, 2H)
Beispiel 3Example 3
Umsetzung von Trimethylbenzoylphenylphosphinsäure mit Ethylenoxid 5Reaction of trimethylbenzoylphenylphosphinic acid with ethylene oxide 5
144 g der Säure aus Beispiel 2 wurde in 500 ml Toluol bei 60 °C gelöst und innerhalb 90 min. mit einer auf -20 °C gekühlten Lösung von 48 g Ethylenoxid in 50 ml Toluol versetzt. Nach 1 h Nachreaktion bei 60 °C zeigte sich in der Dünnschichtchromatogra- 0 fie keine Säure mehr. Die Lösung wurde eingeengt, von einer Trübung abfiltriert und getrocknet. Man isolierte 172 g Umsetzungsprodukt als einheitliches Produkt, Ausbeute quantitativ.144 g of the acid from Example 2 were dissolved in 500 ml of toluene at 60 ° C. and within 90 min. a solution of 48 g of ethylene oxide in 50 ml of toluene, cooled to -20 ° C., is added. After 1 h of post-reaction at 60 ° C, no more acid was found in the thin-layer chromatography. The solution was concentrated, filtered off from a turbidity and dried. 172 g of reaction product were isolated as a single product, yield quantitative.
Elementaranalyse: 66,5 % C, 6,6 % H, 9,1 % PElemental analysis: 66.5% C, 6.6% H, 9.1% P
Beispiel 4Example 4
Umsetzung von Trimethylbenzoylphenylphosphinsäure mit Propyleno- xidReaction of trimethylbenzoylphenylphosphinic acid with propylene oxide
28,8 g der Säure aus Beispiel 2 wurde in 100 ml Toluol bei 60 °C gelöst und innerhalb 45 min. mit einer auf -20 °C gekühlten Lösung von 15.9 g Propylenoxid in 50 ml Toluol versetzt. Nach 1 h Nachreaktion bei 60 °C zeigte sich in der Dünnschichtchromatogra- fie keine Säure mehr. Die Lösung wurde eingeengt, in Diethylether aufgenommen, von einer Trübung abfiltriert und getrocknet. Man isolierte 34,5 g Trimethylbenzoylphenylphosphinsäure-2-hy- droxy-1-propylester als einheitliches Produkt, Ausbeute quantitativ.28.8 g of the acid from Example 2 were dissolved in 100 ml of toluene at 60 ° C. and within 45 min. a solution of 15.9 g of propylene oxide in 50 ml of toluene, cooled to -20 ° C., is added. After 1 hour of post-reaction at 60 ° C, no more acid was found in the thin-layer chromatography. The solution was concentrated, taken up in diethyl ether, filtered off from a turbidity and dried. 34.5 g of trimethylbenzoylphenylphosphinic acid 2-hy were isolated. droxy-1-propyl ester as a single product, quantitative yield.
Elementaranalyse: 67,1 % C, 6,8 % H, 8,9 % PElemental analysis: 67.1% C, 6.8% H, 8.9% P
55
Beispiel 5Example 5
Umsetzung von Trimethylbenzoylphenylphosphinsäure mit i-Butyleno- xidReaction of trimethylbenzoylphenylphosphinic acid with i-butylene oxide
1010
14.4 g der Säure aus Beispiel 2 wurde in 50 ml Toluol bei 60 °C gelöst und innerhalb 45 min. mit einer Lösung von 7,8 g i-Butyle- noxid in 25 ml Toluol versetzt. Nach 1 h Nachreaktion bei 60 °C zeigte sich in der Dünnschichtchromatografie keine Säure mehr.14.4 g of the acid from Example 2 was dissolved in 50 ml of toluene at 60 ° C and within 45 min. with a solution of 7.8 g of i-butylene oxide in 25 ml of toluene. After 1 h of post-reaction at 60 ° C, no more acid was found in the thin layer chromatography.
15 Die Lösung wurde eingeengt, in Diethylether aufgenommen, von einer Trübung abfiltriert und getrocknet. Man isolierte 17,6 g Tri- methylbenzoylphenylphosphinsäure-2-hydroxy-2-isobutylester als einheitliches Produkt, Ausbeute 98 % der Theorie.15 The solution was concentrated, taken up in diethyl ether, filtered off from a turbidity and dried. 17.6 g of trimethylbenzoylphenylphosphinic acid 2-hydroxy-2-isobutyl ester were isolated as a single product, yield 98% of theory.
20 Beispiel 620 Example 6
Umsetzung des Hydroxyethylesters aus Beispiel 3 mit MaleinsäureanhydridReaction of the hydroxyethyl ester from Example 3 with maleic anhydride
25 19,9 g Umsetzungsproduktes aus Beispiel 3 wurde portionsweise mit insgesamt 7,41 g Maleinsäureanhydrid versetzt. Nach 4 h bei 85 °C war das Ausgangsmaterial abreagiert. Nach Aufarbeitung verblieben19.9 g of the reaction product from Example 3 were mixed in portions with a total of 7.41 g of maleic anhydride. After 4 h at 85 ° C, the starting material had reacted. Remained after working up
24.5 g (95 % der Theorie) einheitliches Produkt.24.5 g (95% of theory) uniform product.
30 Beispiel 730 Example 7
Umsetzung des Hydroxyethylesters aus Beispiel 3 mit Toluy- len-2,4-diisocyanat (TDI)Reaction of the hydroxyethyl ester from Example 3 with toluylene-2,4-diisocyanate (TDI)
35 16,5 g Trimethylbenzoylphenylphosphinsäurehydroxyethylester aus Beispiel 3, 20 mg Dibutylzinndilaurat und 20 ml Essigester wurden mit 4,5 g Toluylendiisocyanat (TDI, 0,5 Mol-Äquivalente) versetzt und 4 h bei 70 °C gerührt. Nach Einengen im Vakuum verblieben 19,8 g einheitliches Diadditionsprodukt, Ausbeute 88 % der Theorie.35 16.5 g of trimethylbenzoylphenylphosphinic acid hydroxyethyl ester from Example 3, 20 mg of dibutyltin dilaurate and 20 ml of ethyl acetate were mixed with 4.5 g of tolylene diisocyanate (TDI, 0.5 molar equivalents) and the mixture was stirred at 70 ° C. for 4 h. After concentration in vacuo, 19.8 g of uniform diaddition product remained, yield 88% of theory.
4040
Elementaranalyse: 63,9 % C, 5,9 %, N 3,6 %, H, 6,6 % P,Elemental analysis: 63.9% C, 5.9%, N 3.6%, H, 6.6% P,
Beispiel 8Example 8
45 Umsetzung des Hydroxyethylesters aus Beispiel 3 mit Hexamethy- len-1, 6-diisocyanat (HDI) 16,6 g Trimethylbenzoylphenylphosphinsäurehydroxyethylester aus Beispiel 3, 20 mg Dibutylzinndilaurat und 20 ml Essigester wurden portionsweise mit insgesamt 4,81 g Hexamethylendiisocyanat (HDI, 0,5 Mol-Äquivalente) versetzt und insgesamt 8 h bei 70 °C gerührt. Nach Einengen im Vakuum verblieben 23,2 g einheitliches Diadditi- onsprodukt, Ausbeute quantitativ.45 Reaction of the hydroxyethyl ester from Example 3 with hexamethylene-1, 6-diisocyanate (HDI) 16.6 g of trimethylbenzoylphenylphosphinic acid hydroxyethyl ester from Example 3, 20 mg of dibutyltin dilaurate and 20 ml of ethyl acetate were added in portions with a total of 4.81 g of hexamethylene diisocyanate (HDI, 0.5 molar equivalents) and the mixture was stirred at 70 ° C. for a total of 8 h. After concentration in vacuo, 23.2 g of uniform diaddition product remained, yield quantitative.
Elementaranalyse: 61 , 9 % C, 6 , 6 % H, 3,4 %, N, 6,5 % PElemental analysis: 61.9% C, 6.6% H, 3.4%, N, 6.5% P
Beispiel 9Example 9
Umsetzung des Hydroxyethylesters aus Beispiel 3 mit IsophorondiamindiisocyanatReaction of the hydroxyethyl ester from Example 3 with isophoronediamine diisocyanate
9,96 g Trimethylbenzoylphenylphosphinsäurehydroxyethylester aus Beispiel 3 wurde in 30 ml Toluol gelöst und mit 6,66 g Isophorondiamindiisocyanat (1 Mol-Äquivalent) 4 h bei 70 °C gerührt. Nach Einengen im Vakuum verblieben 16,9 g einheitliches Monoadditions- produkt, Ausbeute quantitativ.9.96 g of trimethylbenzoylphenylphosphinic acid hydroxyethyl ester from Example 3 was dissolved in 30 ml of toluene and stirred with 6.66 g of isophoronediamine diisocyanate (1 mol equivalent) at 70 ° C. for 4 h. After concentration in vacuo, 16.9 g of uniform monoaddition product remained, yield quantitative.
Elementaranalyse: 65,1 % C, 7,03 % H, 5,1 % N, 5,3 % PElemental analysis: 65.1% C, 7.03% H, 5.1% N, 5.3% P
Beispiel 10Example 10
Partielle Hydrolyse des Mono-Isocyanats aus Beispiel 9Partial hydrolysis of the mono-isocyanate from Example 9
Zu einer Mischung aus 110 ml 5 %-iger Salzsäure und 100 ml THF wurde eine Lösung von 16,6 g des Mono-Isocyanats aus Beispiel 9 in 20 ml THF zugegeben und 3 Tage bei 20 °C und 15 h bei 40 °C ge- rührt. Die Reaktionsmischung wurde mit 1 1 Wasser versetzt und leicht alkalisch gestellt (pH 8 - 9) . Die Mischung wurde zweimal mit je 200 ml Methylenchlorid extrahiert, getrocknet und eingeengt. Es verblieben 11,6 g einheitliches Produkt (73 % der Theorie) .A solution of 16.6 g of the mono-isocyanate from Example 9 in 20 ml of THF was added to a mixture of 110 ml of 5% hydrochloric acid and 100 ml of THF, and the mixture was stirred for 3 days at 20 ° C. and for 15 hours at 40 ° C. - stirs. The reaction mixture was mixed with 1 1 of water and made slightly alkaline (pH 8-9). The mixture was extracted twice with 200 ml of methylene chloride, dried and concentrated. There remained 11.6 g of uniform product (73% of theory).
Elementaranalyse: 63,9 % C, 7,5 % H, 4, 8 % N, 5,2 % PElemental analysis: 63.9% C, 7.5% H, 4.8% N, 5.2% P
Beispiel 11Example 11
TrimethylbenzoylphenylphosphinsäurechloridTrimethylbenzoylphenylphosphinsäurechlorid
250 g der Säure aus Beispiel 2 wurde in 670 Toluol suspendiert und mit 102,6 g Pyridin gelöst. Zu dem Reaktionsgemisch wurde bei 60 °C innerhalb von 1 h 1546 g Thionylchlorid zugetropft. Nach 3 h Nachreaktionszeit wurde die rotbraune Emulsion auf 0 °C abgekühlt und die rostbraunen Kristalle abfiltriert. Die verbleibende Lö- sung wurde im Vakuum eingeengt. Auswaage: 265 g (91 % der Theorie) .250 g of the acid from Example 2 were suspended in 670 toluene and dissolved with 102.6 g of pyridine. 1546 g of thionyl chloride were added dropwise to the reaction mixture at 60 ° C. in the course of 1 h. After a reaction time of 3 h, the red-brown emulsion was cooled to 0 ° C. and the rust-brown crystals were filtered off. The remaining solution solution was concentrated in vacuo. Weight: 265 g (91% of theory).
31P-NMR (d6-DMSO) : δ (ppm) = 28,4 31 P NMR (d 6 -DMSO): δ (ppm) = 28.4
iH-NMR (d6-DMSO) : δ (ppm) = 1.7 (s, 6H) , 1.8 (s, 3H) , 6.4 (s, 2H; Mesityl-CH) , 7.15 (m, 2H) , 7.25 (m, 1H) , 7.55 (m, 2H) i H-NMR (d 6 -DMSO): δ (ppm) = 1.7 (s, 6H), 1.8 (s, 3H), 6.4 (s, 2H; mesityl-CH), 7.15 (m, 2H), 7.25 ( m, 1H), 7.55 (m, 2H)
Beispiel 12Example 12
Umsetzung des Chlorides aus Beispiel 11 mit HydroxyethylacrylatReaction of the chloride from Example 11 with hydroxyethyl acrylate
Eine Lösung aus 100 ml Toluol, 7,34 g Triethylamin und 19,07 g des Chlorides aus Beispiel 11 wurde unter Stickstoffatmosphäre auf 50 °C erwärmt. Innerhalb von 30 min. wurden 6,01 g Hydroxyethylacrylat portionsweise zudosiert. Die Temperatur stieg bis auf 60 °C an. Nach weiteren zwei Stunden bei 50 °C wurde das Reaktionsgemisch auf Raumtemperatur abgekühlt und mit 20 ml vollentsalztem Wasser versetzt. Die organische Phase wurde dreimal mit je 30 ml gesättigter Kochsalzlösung extrahiert. Die über Natriumsulfat getrocknete organische Phase wurde zur Trockne eingeengt. Man erhielt 18,52 g des Produktes als bräunliches Öl (Reingehalt 98 %; Ausbeute 91 % d. Theorie) .A solution of 100 ml of toluene, 7.34 g of triethylamine and 19.07 g of the chloride from Example 11 was heated to 50 ° C. under a nitrogen atmosphere. Within 30 min. 6.01 g of hydroxyethyl acrylate were added in portions. The temperature rose to 60 ° C. After a further two hours at 50 ° C., the reaction mixture was cooled to room temperature and 20 ml of deionized water were added. The organic phase was extracted three times with 30 ml of saturated sodium chloride solution. The organic phase dried over sodium sulfate was evaporated to dryness. 18.52 g of the product were obtained as a brownish oil (purity 98%; yield 91% of theory).
Auf analoge Weise ließen sich zahlreiche weitere funktionali- sierte Acylphosphinoxid-Photoinitiatoren herstellen. Beispielhaft sind in Tabelle 1 einige der Produkte aufgeführt und anhand ihrer HPLC-Retentionszeiten charakterisiert .Numerous other functionalized acylphosphine oxide photoinitiators could be prepared in an analogous manner. Examples of some of the products are listed in Table 1 and characterized on the basis of their HPLC retention times.
Tabelle 1: Funktionalisierte Acylphosphinoxid - PhotoinitiatorenTable 1: Functionalized acylphosphine oxide photoinitiators
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0001
n.b. nicht bestimmt HPLC-Analytik : Kontron Instruments HPLC-Pump 422, Lichrosorb 18 7, Bischoff Chromatography, Shimadzu C-R6A Chromatopac, Mition Roy Spectro Monitor 3100 (230 nm) , Acetonitril/Wasser/Phosphor- säure (Verhältnis 570:430:1) bei 1.1 ml/min.
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0001
nb not determined HPLC analysis: Kontron Instruments HPLC-Pump 422, Lichrosorb 18 7, Bischoff Chromatography, Shimadzu C-R6A Chromatopac, Mition Roy Spectro Monitor 3100 (230 nm), acetonitrile / water / phosphoric acid (ratio 570: 430: 1) 1.1 ml / min.
Anwendungsbeispiele LackhärtungApplication examples paint curing
Lacksystempaint system
Als Klarlack getestet wurde eine Harzmischung aus Laromer 8967 (BASF AG, aminfreies epoxidmodifiziertes Polyetheracrylat) und 1 Gew.- % Photoinitiator.A resin mixture of Laromer 8967 (BASF AG, amine-free, epoxy-modified polyether acrylate) and 1% by weight photoinitiator was tested as a clear coat.
Als pigmentiertes System wurde eine Suspension aus 1 Gew.-% des jeweiligen Photoinitiators unter Zusatz von 1 Gew.-% Irgacure®A suspension of 1% by weight of the respective photoinitiator with the addition of 1% by weight of Irgacure® was used as the pigmented system
(Ciba-Spezialitätenchemie) 500 (Mischung aus 1-Hydroxy-cyclohe- xyl-phenylketon und Benzophenon 1/1) , Rutil und Laromer® 8967(Ciba specialty chemistry) 500 (mixture of 1-hydroxy-cyclohexyl phenyl ketone and benzophenone 1/1), rutile and Laromer® 8967
(BASF AG) hergestellt.(BASF AG).
SchichtenhärtungSchichtenhärtung
Bei den Tests zur Schichtenhärtung wurde auf eine Folie der Lackfilm mit einer definierten Schichtdicke (15 bzw. 100 μm) aufgetragen. Der Film wurde bei einer definierten Bandgeschwindigkeit mehrfach durch die Bestrahlungsappratur geschickt. Apparatur: UV- Polymerisationanlage IST UV-Minicure, 300-1-TR; Lampen: lxCK, lx dotiert, Leistung: 80 W/cm.In the tests for layer hardening, the lacquer film was applied to a film with a defined layer thickness (15 or 100 μm). The film was passed through the irradiation apparatus several times at a defined belt speed. Equipment: UV polymerisation system IST UV-Minicure, 300-1-TR; Lamps: lxCK, lx doped, power: 80 W / cm.
Die Härtung des Klarlacks unter Inert (N2, 300 ppm 02,) wurde ana- log durchgeführt, Apparatur: IST UV-Polymerisationanlage,The curing of the clearcoat under inert (N 2 , 300 ppm 0 2 ,) was carried out analogously, apparatus: IST UV polymerization system,
M40-2xl-R-Tr-SLC-SO-inert; Lampe: lx M 400 U2H (CK) , Leistung: 160 W/cmM40-2xl-R-Tr-SLC-SO-inert; Lamp: lx M 400 U2H (CK), power: 160 W / cm
Tiefenhärtungdeep curing
Für Tiefenhärtungstests werden 4,0 g Klarlack in einen Metalldek- kel gegeben. Dieser wird auf das Laufband gelegt und durchlief die Bestrahlungsapparatur (Bandgeschwindigkeit 5 m/s, Lauflänge ca. 2 m). Anschließend wurde der gehärtete (polymerisierte) Teil von der Lösung abgetrennt, mit Aceton gewaschen und die Lackschichtdicke gemessen (Oberflächenhärtung wird vernachlässigt) . Tests (zu Tabelle 2)For deep hardening tests, 4.0 g of clear lacquer are placed in a metal lid. This is placed on the treadmill and passed through the irradiation apparatus (belt speed 5 m / s, barrel length approx. 2 m). The hardened (polymerized) part was then separated from the solution, washed with acetone and the lacquer layer thickness measured (surface hardening is neglected). Tests (for table 2)
Schichtdickenhärtung Klarlacksystem an LuftLayer thickness hardening clear lacquer system in air
la) Schichtdicke 15 um; (lb) lOOμmla) layer thickness 15 µm; (lb) 100 µm
2) Schichtdickenhärtung Klarlacksystem unter Inertatmosphäre2) Layer thickness hardening clear lacquer system under an inert atmosphere
2a) Schichtdicke 15 um; (2b) lOOμm2a) layer thickness 15 µm; (2b) 100 µm
3) Tiefenhärtung Klarlack3) Deep curing clear coat
4) Tiefenhärtung Rutilpigmentierter Lack4) Deep curing rutile pigmented lacquer
Tabelle 2: Testergebnisse StrahlungshärtungTable 2: Radiation curing test results
Figure imgf000086_0001
Figure imgf000087_0001
Figure imgf000086_0001
Figure imgf000087_0001
* [Anzahl Durchläufe bis zur Härtung bei einer Bandgeschwindigkeit von 5 m/min]* [Number of passes until hardening at a belt speed of 5 m / min]
** [Bandgeschwindigkeiten 100 m/min]** [belt speeds 100 m / min]
Man sieht, daß die erfindungsgemäßen Verbindungen ähnliche Aktivität aufweisen, wie Lucirin TPO, in der Tiefenhärtung z.T. sogar besser sind (Spalte 3). It can be seen that the compounds according to the invention have activity similar to that of Lucirin TPO, in some cases in deep curing. are even better (column 3).

Claims

Patentansprüche claims
1 . Acyl- oder Bisacylphosphinderivat gemäß Formel (I ) ,1 . Acyl or bisacylphosphine derivative according to formula (I),
ZZ
Figure imgf000088_0001
Figure imgf000088_0001
worinwherein
R1, R2 Ci - Ci8~Alkyl, gegebenenfalls durch ein oder mehrere Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubstituierte Iminogruppen unterbrochenes C - Ci8~Alkyl, C2 - Cχ8-Alkenyl, C6 - Cι2-Aryl, C5 - Cχ2-Cycloalkyl oder einen fünf- bis sechsgliedrigen, Sauerstoff-, Stickstoff- und/oderR 1 , R 2 Ci - Ci 8 ~ alkyl, optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups C - Ci 8 ~ alkyl, C 2 - Cχ 8 alkenyl, C 6 - Cι 2 aryl, C 5 - Cχ 2 cycloalkyl or a five- to six-membered, oxygen-, nitrogen- and / or
Schwefelatome aufweisenden Heterocyclus , wobei die genannten Reste jeweils durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiert sein können,Heterocycle containing sulfur atoms, where the radicals mentioned can each be substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles,
R2 ferner gegebenenfalls durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiertes Ci - C18-Alkoxy oder R1-(C=Y)-,R 2 furthermore optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles Ci - C 18 alkoxy or R 1 - (C = Y) -,
Y 0, S, NR3, N-OR3 oder N-NR3R4,Y 0, S, NR 3 , N-OR 3 or N-NR 3 R 4 ,
Z 0, S, NR3, N-OR3, N-NR3R4 oder ein freies Elektronenpaar,Z 0, S, NR 3 , N-OR 3 , N-NR 3 R 4 or a free electron pair,
R3 Wasserstoff, Ci bis C4-Alkyl, S03H, Phenyl oder Acetyl,R 3 is hydrogen, Ci to C 4 alkyl, S0 3 H, phenyl or acetyl,
R4 Wasserstoff, Ci bis C-Alkyl, COOR3 oder gegebenenfalls durch Aryl, Alkyl, Aryloxy, Alkyloxy, Heteroatome und/ oder Heterocyclen substituiertes C6 - Cχ -Aryl oder Arylsulfonyl,R 4 is hydrogen, Ci to C-alkyl, COOR 3 or C 6 - Cχ-aryl or arylsulfonyl which is optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles,
X einen n-fach mit Gruppen RG substituierten Spacer,X is a spacer substituted n times with groups RG,
RG eine radikalisch oder kationisch polymerisierbare Gruppe oder eine Gruppe, die in Wechselwirkung mit dem sich bildenden Polymer treten kann und n eine natürliche Zahl von 1 bis 10 undRG is a radical or cationically polymerizable group or a group which can interact with the polymer being formed and n is a natural number from 1 to 10 and
bedeuten .mean.
2. Acyl- oder Bisacylphosphinderivat gemäß Anspruch 1, worin RG . Vinyl, Vinyloxy, 1-Propen-1-yl , l-Propen-2-yl, 2-Buten-2-yl , 3-Methyl-2-Buten-2-yl, 2-Vinylphen-l-yl , 3-Vinylphen-l-yl , 3-Vinylphen-l-yl, 2-Phenylethen-l-yl, 2- (4-Methoxyphe- nyl) -ethen-1-yl, Acryl, Methacryl, Crotonyl, Acryloxy, Acryl- amido, Methacryloxy oder Crotonyloxy oder eine Gruppe -N+R9 3, -OR9, -SR9, COO- oder COOR9 bedeutet, worin R9 jeweils gleich oder unterschiedlich Wasserstoff oder Cι-C -Alkyl, beispielsweise Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl , iso-Bu- tyl, seJ-Butyl oder tert. -Butyl, sein kann.2. acyl or bisacylphosphine derivative according to claim 1, wherein RG. Vinyl, vinyloxy, 1-propen-1-yl, 1-propen-2-yl, 2-buten-2-yl, 3-methyl-2-buten-2-yl, 2-vinylphen-l-yl, 3- Vinylphen-l-yl, 3-vinylphen-l-yl, 2-phenylethen-l-yl, 2- (4-methoxyphenyl) -ethen-1-yl, acrylic, methacrylic, crotonyl, acryloxy, acrylamido, Methacryloxy or crotonyloxy or a group -N + R 9 3 , -OR 9 , -SR 9 , COO- or COOR 9 , in which R 9 in each case the same or different hydrogen or -CC alkyl, for example methyl, ethyl, n- Propyl, iso-propyl, n-butyl, iso-butyl, seJ-butyl or tert. -Butyl, can be.
3. Acyl- oder Bisacylphosphinderivat gemäß Anspruch 1, worin RG Vinyl, l-Propen-2-yl, Acryl (H2C=CH (CO) -) , Acryloxi3. acyl or bisacylphosphine derivative according to claim 1, wherein RG vinyl, l-propen-2-yl, acrylic (H 2 C = CH (CO) -), Acryloxi
(H2C=CH(CO)0-) , Methacryloxy, Acrylamido, Methacrylamido, Hydroxy (-OH) , Mercapto (-SH) , Amino (-NH2), Carboxyl (-COOH) oder Carboxylat (-C00-) ist.(H 2 C = CH (CO) 0-), methacryloxy, acrylamido, methacrylamido, hydroxy (-OH), mercapto (-SH), amino (-NH 2 ), carboxyl (-COOH) or carboxylate (-C00-) is.
4. Acyl- oder Bisacylphosphinderivat gemäß einem der vorstehenden Ansprüche, worin X unsubstituiertes oder mit Halogen, Ci-Cs-Alkyl, C2-Cβ-Alkenyl, Carboxy, Carboxy-Cι-C8-Alkyl, Cι-C2rj-Acyl, Ci-Cs-Alkoxy, C6-Cι2-Aryl, Hydroxyl , hydroxysub- stituiertem Ci-Cs-Alkyl oder n-fach von Gruppen RG substituiertes C6~Cι2-Arylen, C3-Cι2-Cycloalkylen, Cι-C2rj-Alkylen oder durch ein oder mehrere Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubsti- tuierte Iminogruppen und/oder durch eine oder mehrere -(CO)-, -0(C0)0-, -(NH)(C0)0-, -O(COHNH)-, -O(CO)- oder -(CO)O-Grup- pen unterbrochenes C2-C20-Alkylen bedeutet.4. acyl or bisacylphosphine derivative according to any one of the preceding claims, wherein X is unsubstituted or with halogen, Ci-Cs-alkyl, C 2 -Cβ-alkenyl, carboxy, carboxy -CC-C 8 alkyl, -C-C 2 r j - Acyl, Ci-Cs-alkoxy, C 6 -C 2 -aryl, hydroxyl, hydroxy-substituted Ci-Cs-alkyl or n-fold substituted by groups RG C 6 -C 2 -arylene, C 3 -C 2 -cycloalkylene, C 1 -C 2 -alkylene or by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups and / or by one or more - (CO) -, -0 (C0) 0- , - (NH) (C0) 0-, -O (COHNH) -, -O (CO) - or - (CO) O groups means interrupted C 2 -C 20 alkylene.
5. Acyl- oder Bisacylphosphinderivat gemäß einem der Ansprüche 1 bis 3, worin X für5. acyl or bisacylphosphine derivative according to any one of claims 1 to 3, wherein X is
-Z1- [ (Ai ) a-Z2 ] c" [ ( 2 ) b-Z3 ] d-Z 1 - [(Ai) a -Z 2 ] c "[( 2 ) bZ 3 ] d
steht, worinstands in what
Z1, Z2, und Z3 jeweils unabhängig voneinander für eine Einfachbindung, -0-, -S-, -N(R8)-, -(CO)-, -(C0)0-, -(CO)N(R8) -O-(CO)-, -N(R8)-(C0)- oder -N(R8) - (CO) 0- stehen, Ax und A2 unabhängig voneinander Ci - C -Alkylen, C3 - Cι2-Cy- cloalkylen, Phenylen, Phenylen-Ci - C -Alkylen oder Ci - C -Alkylen-Phenylen-Cι - C -Alkylen bedeuten,Z 1 , Z 2 , and Z 3 each independently for a single bond, -0-, -S-, -N (R 8 ) -, - (CO) -, - (C0) 0-, - (CO) N (R 8 ) -O- (CO) -, -N (R 8 ) - (C0) - or -N (R 8 ) - (CO) 0-, A x and A 2 independently of one another are Ci - C alkylene, C 3 - C 2 -cycloalkylene, phenylene, phenylene-Ci - C-alkylene or Ci - C-alkylene-phenylene-Cι - C alkylene,
a,b,c,d unabhängig voneinander für die Zahlen 0 bis 4 stehen unda, b, c, d independently of one another represent the numbers 0 to 4 and
R8 Wasserstoff, Ci bis Ciβ-Alkyl oder Phenyl ist.R 8 is hydrogen, Ci to Ciβ-alkyl or phenyl.
6. Acyl- oder Bisacylphosphinderivat gemäß einem der Ansprüche 1 bis 3, worin X 1,2-Ethylen, 1, 2-Propylen, 1, 3-Propylen, 1,4-Butylen, 1,6-Hexylen, 2-Methyl-l, 3-Propylen, 2,2-Dime- thyl-1, 3-Propylen, 2 , 2-Dimethyl-l, 4-butylen, 1-Oxa-l , 3-propy- len, 1, 4-Dioxa-l, 6-hexylen, 1, 4, 7-Trioxa-l, 9-nonylen, 1-Oxa-l, 4-butylen, 1, 5-Dioxa-l , 8-octylen, 1-Oxa-l, 5-pentylen, 1-Oxa-l, 7-heptylen, 1, 6-Dioxa-l, 10-decylen, l-0xa-3-me- thyl-1, 3-propylen, l-0xa-3-methyl-l, 4-butylen, l-0xa-3 , 3-di- methyl-1 , 4-butylen, l-Oxa-3 , 3-dimethyl-l , 5-pentylen, 1, 4-Dioxa-3 , 6-dimethyl-l, 6-hexylen, 1-Oxa-2-methyl-1 , 3-propy- len, 1, 4-Dioxa-2, 5-dimethyl-l, 6-hexylen,6. acyl or bisacylphosphine derivative according to any one of claims 1 to 3, wherein X is 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene, 1,6-hexylene, 2-methyl- 1,3-propylene, 2,2-dimethyl-1,3-propylene, 2,2-dimethyl-1,4-butylene, 1-oxa-1,3-propylene, 1,4-dioxa- l, 6-hexylene, 1, 4, 7-trioxa-l, 9-nonylene, 1-oxa-l, 4-butylene, 1, 5-dioxa-l, 8-octylene, 1-oxa-l, 5- pentylene, 1-oxa-l, 7-heptylene, 1, 6-dioxa-l, 10-decylene, l-0xa-3-methyl-1, 3-propylene, l-0xa-3-methyl-l, 4-butylene, l-0xa-3, 3-dimethyl-1, 4-butylene, l-oxa-3, 3-dimethyl-l, 5-pentylene, 1, 4-dioxa-3, 6-dimethyl- 1, 6-hexylene, 1-oxa-2-methyl-1, 3-propylene, 1, 4-dioxa-2, 5-dimethyl-1, 6-hexylene,
1-Oxa-l, 5-pent-3-enylen, 1-Oxa-l, 5-pent-3-inylen, 1,2-, 1,3- oder 1, 4-Cyclohexylen, 1,2- oder 1, 3-Cyclopentylen, 1,2-, 1,3- oder 1,4-Phenylen oder 4 , 4 ' -Biphenylen bedeutet.1-oxa-l, 5-pent-3-enylene, 1-oxa-l, 5-pent-3-enylene, 1,2-, 1,3- or 1,4-cyclohexylene, 1,2- or 1 , 3-cyclopentylene, 1,2-, 1,3- or 1,4-phenylene or 4,4'-biphenylene.
7. Acyl- oder Bisacylphosphinderivat gemäß einem der vorstehenden Ansprüche, worin7. acyl or bisacylphosphine derivative according to any one of the preceding claims, wherein
R1 Phenyl, 2 , 6-Dichlorphenyl , 2 , 4 , 6-Trichlorphenyl , 2,6-Di- methylphenyl , 2, 4, 6-Trimethylphenyl oder 2 , 6-Dimethoxy- phenyl ,R 1 is phenyl, 2, 6-dichlorophenyl, 2, 4, 6-trichlorophenyl, 2,6-dimethylphenyl, 2, 4, 6-trimethylphenyl or 2, 6-dimethoxyphenyl,
R2 Methoxy, Ethoxy, n-Butyloxy, Phenyl, 4-Diphenylyl, 2-, 3- oder 4-Chlorphenyl, 2-, 3- oder 4-Methylphenyl, 2-, 3- oder 4-Methoxyphenyl oder 2-, 3- oder 4-Ethoxyphenyl,R 2 methoxy, ethoxy, n-butyloxy, phenyl, 4-diphenylyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-methoxyphenyl or 2-, 3rd - or 4-ethoxyphenyl,
0 und0 and
bedeuten.mean.
8. Verfahren zur Herstellung eines Acyl- oder Bisacylphosphinde- rivats der Formel (I) gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß man eine Verbindung H-X-RGn oder θχ-RGn mit einer Verbindung der Formel (III) ,
Figure imgf000091_0001
worin R1, R2 , X, Y, Z und RG die in den Ansprüchen 1 bis 7 angegebenen Bedeutungen haben und FG eine Abgangsgruppe bedeutet, umsetzt.8. A process for the preparation of an acyl or bisacylphosphine derivative of the formula (I) according to any one of the preceding claims, characterized in that a compound HX-RG n or θχ-RG n with a compound of the formula (III),
Figure imgf000091_0001
wherein R 1 , R 2 , X, Y, Z and RG have the meanings given in claims 1 to 7 and FG means a leaving group.
9. Dimeres Acyl- oder Bisacylphosphinderivat gemäß Formel (II)9. Dimeric acyl or bisacylphosphine derivative according to formula (II)
Figure imgf000091_0002
Figure imgf000091_0002
worinwherein
worin R1 , R2 , Y und Z die in Anspruch 1 genannten Bedeutungen haben und R1', R2', Y' und Z' die gleichen Bedeutungen haben wie R1, R2, Y und Z, jedoch von diesen verschieden sein können,wherein R 1 , R 2 , Y and Z have the meanings given in claim 1 and R 1 ', R 2 ', Y 'and Z' have the same meanings as R 1 , R 2 , Y and Z, but different from these could be,
X wie in den Ansprüchen 1 oder 4 bis 6 definiert ist, undX is as defined in claims 1 or 4 to 6, and
Het1 und Het2 unabhängig voneinander 0, S oder NR9 undHet 1 and Het 2 independently of one another 0, S or NR 9 and
R9 jeweils gleich oder unterschiedlich Wasserstoff oderR 9 is the same or different hydrogen or
Cι-C -Alkyl, beispielsweise Methyl, Ethyl, n-Propyl, iso-Pro- pyl, n-Butyl, iso-Butyl, seJc-Butyl oder tert. -Butyl,C 1 -C 4 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, seJc-butyl or tert. butyl,
bedeuten .mean.
10. Verfahren zur Herstellung von dimeren Acyl- und Bisacylphosphinderivaten gemäß Anspruch 9, dadurch gekennzeichnet, daß man einen Stoff (III) , wie in Anspruch 8 definiert, mit einer Verbindung H-Heti-X-He^-H, ©Heti-X-He^-H, H-Heti-X-Het2© oder ©Het1-X-Het2θ umsetzt, wobei X, Het1 und Het2 wie in den Ansprüchen 1, 4 bis 6 oder 9 definiert sind.10. A process for the preparation of dimeric acyl and bisacylphosphine derivatives according to claim 9, characterized in that a substance (III), as defined in claim 8, with a compound H-Het i -X-He ^ -H, © Het i -X-He ^ -H, H-Het i -X-Het 2 © or © Het 1 -X-Het 2θ , where X, Het 1 and Het 2 are as defined in claims 1, 4 to 6 or 9 ,
11. Verfahren zur Herstellung von dimeren Acyl- und Bisacylphosphinderivaten gemäß Anspruch 9, dadurch gekennzeichnet, daß man Verbindungen der Formel (IV) ,
Figure imgf000092_0001
11. A process for the preparation of dimeric acyl and bisacylphosphine derivatives according to claim 9, characterized in that compounds of the formula (IV),
Figure imgf000092_0001
worin R1 ' , R2 ' , X, Y' , Z', Het1 und Het2 wie in Anspruch 9 de- 10 finiert sind,wherein R 1 ', R 2 ', X, Y ', Z', Het 1 and Het 2 are as defined in claim 9,
mit Verbindungen der Formel (III) , wie in Anspruch 8 definiert, umsetzt.with compounds of formula (III) as defined in claim 8.
15 12. Verbindung, erhältlich durch Umsetzung von Acyl- und Bisacylphosphinderivaten gemäß Formel (I) oder (IV) , wie in Anspruch 1 oder 11 definiert, mit Verbindungen, die Gruppen enthalten, die mit der Gruppe -RG oder -Het -H eine chemische Bindung einzugehen vermögen.15 12. Compound obtainable by reacting acyl and bisacylphosphine derivatives according to formula (I) or (IV), as defined in claim 1 or 11, with compounds which contain groups which are one with the group -RG or -Het -H can form chemical bonds.
2020
13. Verbindung gemäß Anspruch 12, dadurch gekennzeichnet, daß man, mit Verbindungen umsetzt, die Isocyanat-, Epoxid-, Anhydrid-, Säurechlorid-, Ester-, Säure-, Carbonat-, Aldehyd-, α, ß-ungesättigte Carbonyl-, Chloralkyl-, Bromalkyl-, Iodal- 25 kyl- oder Nitrilgruppen Gruppen enthalten.13. A compound according to claim 12, characterized in that, reacted with compounds, the isocyanate, epoxy, anhydride, acid chloride, ester, acid, carbonate, aldehyde, α, β-unsaturated carbonyl, Chloroalkyl, bromoalkyl, iodal, 25 kyl or nitrile groups contain groups.
14. Acyl- und Bisacylphosphinderivate gemäß Formel (Va) ,14. acyl and bisacylphosphine derivatives according to formula (Va),
Figure imgf000092_0002
Figure imgf000092_0002
35 worin35 where
R1', R2', X, Y', Z', Het1 und Het2 wie in Anspruch 9 definiert sind undR 1 ', R 2 ', X, Y ', Z', Het 1 and Het 2 are as defined in claim 9 and
0 R11 1,6-Hexylen, 3 , 5 , 5-Trimethyl-l , 3-cyclohexylen, 1-Me- thyl-2 , 4-phenyl, 1-Methyl-2 , 6-phenyl, 4 , 4 ' -Diphenylmethy- len, 2 , 4 '-Diphenylmethylen oder 2 ' , 4-Diphenylmethylen bedeutet.0 R 11 1,6-hexylene, 3, 5, 5-trimethyl-l, 3-cyclohexylene, 1-methyl-2, 4-phenyl, 1-methyl-2, 6-phenyl, 4, 4 '- Diphenylmethylene, 2, 4 '-diphenylmethylene or 2', 4-diphenylmethylene.
5 5
15. Acyl- und Bisacylphosphinderivate gemäß Formel (Vb) ,15. acyl and bisacylphosphine derivatives according to formula (Vb),
Figure imgf000093_0001
worin
Figure imgf000093_0001
wherein
R1', R2', X, Y', Z', Het1 und Het2 wie in Anspruch 9 definiert sind.R 1 ', R 2 ', X, Y ', Z', Het 1 and Het 2 are as defined in claim 9.
16. Acyl- und Bisacylphosphinderivate gemäß Formel (Vc) ,16. acyl and bisacylphosphine derivatives according to formula (Vc),
w
Figure imgf000093_0002
w
Figure imgf000093_0002
R1', R2', X, Y', Z', Het1 und Het2 wie in Anspruch 9 definiert sind undR 1 ', R 2 ', X, Y ', Z', Het 1 and Het 2 are as defined in claim 9 and
R19 Wasserstoff oder Methyl bedeutet. R 19 represents hydrogen or methyl.
17. Verfahren zur Herstellung von Verbindungen gemäß Anspruch 12, dadurch gekennzeichnet, daß man Stoffe gemäß Formel (IV) mit isocyanat- oder epoxygruppenhaltigen Verbindungen umsetzt.17. A process for the preparation of compounds according to claim 12, characterized in that substances of the formula (IV) are reacted with compounds containing isocyanate or epoxy groups.
18. Verwendung von Stoffen gemäß einem der Ansprüche 1 - 7, 9 oder 12 - 16 als Photoinitiator.18. Use of substances according to one of claims 1-7, 9 or 12-16 as a photoinitiator.
19. Strahlungshärtbare Zusammensetzungen, erhältlich durch Umsetzung mindestens eines Stoffes gemäß einem der vorstehenden Ansprüche mit einer reaktive Zentren und/oder polare Gruppen enthaltenden Verbindung.19. Radiation-curable compositions obtainable by reacting at least one substance according to one of the preceding claims with a compound containing reactive centers and / or polar groups.
20. Strahlungshärtbare Zusammensetzung, enthaltend einen Photoinitiator gemäß einem der Ansprüche 1 - 7, 9 oder 12 - 16.20. Radiation-curable composition containing a photoinitiator according to any one of claims 1-7, 9 or 12-16.
21. Verbindung, erhältlich durch Umsetzung von Verbindung (III) mit Photoinitiatoren, die reaktive Gruppen enthalten. 21. A compound obtainable by reacting compound (III) with photoinitiators containing reactive groups.
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